N-Phenylsulfonyl-N&#39;-triazinyl-ureas

ABSTRACT

N-Phenylsulfonyl-N&#39;-pyrimidinyl- and -triazinyl-ureas of the general formula ##STR1## and the salts of these compounds with amines, alkali metal or alkaline earth metal bases or quaternary ammonium bases have good pre-emergence and post-emergence selective herbicidal properties and growth-regulating properties. 
     In this formula, A is a C 1  -C 6  -alkyl radical which is substituted by halogen, C 1  -C 4  -alkoxy, C 1  -C 4  -alkylthio, C 1  -C 4  -alkylsulfinyl, C 1  -C 4  -alkylsulfonyl, C 1  -C 4  -halogenoalkoxy, C 1  -C 4  -halogenoalkylthio, C 1  -C 4  -halogenoalkylsulfinyl or C 1  -C 4  -halogenoalkylsulfonyl, or is a C 2  -C 6  -alkenyl radical substituted by the above radicals, E is the methine group or nitrogen, X is oxygen, sulfur or a sulfinyl or sulfonyl bridge, Z is oxygen or sulfur, m is the number one or two, R 1  is hydrogen, halogen, C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl or a --Y--R 5  radical, R 2  is hydrogen, halogen, C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl, C 1  -C 4  -halogenoalkyl or a --Y--R 5 , --COOR 6 , --NO 2  or --CO--NR 7  --R 8  radical, R 3  is hydrogen, C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, C 1  -C 4  -alkylthio, C 1  -C 4  -halogenoalkyl, halogen, C 1  -C 4  -halogenoalkoxy or alkoxyalkyl having not more than 4 carbon atoms, R 4  is C 1  -C 4  -halogenoalkoxy or C 1  -C 4  -halogenoalkylthio, R 5  and R 6  are each C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl or C 2  -C 6  -alkynyl R 7  and R 8  independently of one another are hydrogen, C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl or C 2  -C 6  -alkynyl and Y is oxygen, sulfur or a sulfinyl or sulfonyl bridge, and A can also be an unsubstituted C 2  -C 6  -alkenyl radical if X is simultaneously oxygen.

The present invention relates to novel herbicidally active and plantgrowth-regulating N-phenylsulfonyl-N'-pyrimidinyl- and -triazinyl-ureas,processes for their preparation, compositions containing them as activesubstances, and their use for controlling weeds, in particular forselectively controlling weeds in crops of useful plants or forregulating and inhibiting plant growth.

The N-phenylsulfonyl-N'-pyrimidinyl- and -triazinyl-ureas according tothe invention are those of the general formula I ##STR2## in which A isa C₁ -C₆ -alkyl radical which is substituted by halogen, C₁ -C₄ -alkoxy,C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulfinyl, C₁ -C₄ -alkylsulfonyl, C₁ -C₄-halogenoalkoxy, C₁ -C₄ -halogenoalkylthio, C₁ -C₄-halogenoalkylsulfinyl or C₁ -C₄ -halogenoalkylsulfonyl, or is a C₂ -C₆-alkenyl radical substituted by the above radicals, E is the methinegroup or nitrogen, X is oxygen, sulfur or a sulfinyl or sulfonyl bridge,Z is oxygen or sulfur, m is the number one or two, R₁ is hydrogen,halogen, C₁ -C₅ -alkyl, C₂ -C₅ -alkenyl or a --Y-R₅ radical, R₂ ishydrogen, halogen, C₁ -C₅ -alkyl, C₂ -C₅ -alkenyl, C₁ -C₄ -halogenoalkylor a --Y-R₅, --COOR₆, --NO₂ or --CO-NR₇ -R₈ radical, R₃ is hydrogen, C₁-C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -halogenoalkyl, C₁-C₄ -halogenoalkoxy, halogen or alkoxyalkyl having not more than 4carbon atoms, R₄ is C₁ -C₄ -halogenoalkoxy or C₁ -C₄ -halogenoalkylthio,R₅ and R₆ are each C₁ -C₅ -alkyl, C₂ -C₅ -alkenyl or C₂ -C₆ -alkynyl, R₇and R₈ independently of one another are hydrogen, C₁ -C₅ -alkyl, C₂ -C₅-alkenyl or C₂ -C₆ -alkynyl and Y is oxygen, sulfur or a sulfinyl orsulfonyl bridge, and in which A can also be an unsubstituted C₂ -C₆-alkenyl radical if X is simultaneously oxygen, and the salts of thesecompounds.

Urea compounds, triazine compounds and pyrimidine compounds having aherbicidal action are generally known.Arylsulfamoyl-heterocyclyl-aminocarbamoyl compounds having a herbicidaland plant growth regulating action have recently been disclosed, forexample in Dutch Pat. No. 121,788, European Patent Publications Nos.9,419 and 23,422, U.S. Pat. No. 4,127,405, German Offenlegungsschrift2,715,786 and French Patent Specification 1,468,747.

In the definitions, alkyl is to be understood as meaning straight-chainor branched alkyl, for example methyl ethyl, n-propyl, i-propyl, thefour isomeric butyl radicals, n-amyl, i-amyl, 2-amyl, 3-amyl, n-hexyland i-hexyl.

Alkoxy is to be understood as meaning methoxy, ethoxy, n-propoxy,i-propoxy and the four isomeric butoxy radicals, but especially methoxy,ethoxy or i-propoxy.

Examples of alkylthio are methylthio, ethylthio, n-propylthio,i-propylthio and n-butylthio, but especially methylthio and ethylthio.

Examples of alkenyl radicals are vinyl, allyl, isopropenyl, prop-1-enyl,but-1-enyl, but-2-enyl, but-3-enyl, isobut-1-enyl, isobut-2-enyl,pent-1-enyl, pent-2-enyl, pent-3-enyl and pent-4-enyl, but especiallyvinyl, allyl and pent-4-enyl.

Examples of alkylsulfinyl are methylsulfinyl, ethylsulfinyl,n-propylsulfinyl and n-butylsulfinyl, but especially methylsulfinyl andethylsulfinyl.

Examples of alkylsulfonyl are methylsulfonyl, ethylsulfonyl,n-propylsulfonyl and n-butylsulfonyl, but especially methylsulfonyl andethylsulfonyl.

Halogen in the definitions and in halogeno-alkyl, -alkoxy,-alkylsulfinyl, -alkylsulfonyl and -alkylthio is to be understood asmeaning fluorine, chlorine or bromine, but preferably fluorine orchlorine.

Preferred halogenoalkyl radicals, which may also be constituents oflarger substituent groups, for example of a halogenoalkoxy orhalogenoalkylthio radical, are difluoromethyl, trifluoromethyl,perfluoroethyl, 2,2,2-trifluoroethyl, chlorofluoromethyl,bromofluoromethyl, 2-chloroethyl, 1,1,2,2-tetrafluoroethyl,2-fluoroethyl, 2,2,2-trichloroethyl, bromodifluoromethyl,chlorodifluoromethyl, 1,1,2-trifluoro-2-chloroethyl,1,1,2-trifluoro-2-bromoethyl and 1,1,2,3,3,3-hexafluoropropyl, butespecially difluoromethyl, 2,2,2-trifluoroethyl and perfluoroethyl.

Alkynyl radicals in the definitions of the above symbols are as a rulepropargyl, but-2-ynyl, but-3-ynyl and the isomeric pentynyl and hexynylradicals, but the alkynyl radical is preferably propargyl or but-2- or-3-ynyl.

The invention also relates to the salts which the compounds of theformula I can form with amines, alkali metal and alkaline earth metalbases and quaternary ammonium bases.

Of the alkali metal and alkaline earth metal hydroxides, the hydroxidesof lithium, sodium, potassium, magnesium and calcium, but especiallythose of sodium and potassium, are preferred salt-forming agents.

Examples of amines suitable for salt formation are primary secondary andtertiary aliphatic and aromatic amines, such as methylamine, ethylamine,propylamine, ipropylamine, the four isomeric butylamines, dimethylamine,diethylamine, diethanolamine, dipropylamine, diisopropylamine,di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine,triethylamine, tripropylamine, quinuclidine, pyridine, quinoline andi-quinoline, but especially ethylamine, propylamine, diethylamine andtriethylamine, and in particular iso-propylamine and diethanolamine.

Examples of quaternary ammonium bases are, in general, the cations ofammonium halide salts, for example the tetramethylammonium cation, thetrimethylbenzylammonium cation, the triethylbenzylammonium cation, thetetraethylammonium cation, the trimethylethylammonium cation and theammonium cation.

Preferred compounds of the formula I according to the invention arethose in which (a) X or (b) Z is oxygen or (c) m is the number one and(d) the radicals R₃ and R₄ together contain not more than 4 carbonatoms.

Combination of the preferred features gives the following furtherpreferred group of compounds of the formula I in which X and Z areoxygen, m is the number one and the radical -X-A occupies theortho-position relative to the sulfonyl group.

Within this group, preferred compounds are moreover those in which theradicals R₃ and R₄ together contain not more than 4 carbon atoms.

Particularly preferred compounds within this subgroup are those in whichR₄ is halogenoethoxy or halogenomethoxy. Of these, those in which R₄ isthe 2,2,2-trifluoroethoxy radical or the difluoromethoxy radical are inturn preferred.

Specific preferred compounds areN-(2-difluoromethoxyphenyl-sulfonyl)-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]-urea,N-[2-(2-chloroethoxy)-phenylsulfonyl]-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]-urea,N-(2-trifluoromethoxyphenylsulfonyl)-N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-ureaandN-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-urea.

The compounds of the formula I are prepared in an inert organic solvent.

In a first process, the compounds of the formula I are obtained by aprocedure which comprises reacting a phenylsulfonamide of the formula II##STR3## in which A, R₁, R₂, X and m are as defined under formula I,with an N-pyrimidinyl- or -triazinyl-carbamate of the formula III##STR4## in which E, R₃, R₄ and Z are as defined under formula I and R₁₁is hydrogen, halogen, nitro or C₁ -C₃ -alkyl, in the presence of a base.

In a second process, compounds of the formula I are obtained by aprocedure which comprises reacting a phenylsulfonyl isocyanate orisothiocyanate of the formula IV ##STR5## in which A, R₁, R₂, m, X and Zare as defined under formula I, with an amine of the formula V ##STR6##in which E, R₃ and R₄ are as defined under formula I, in the presence orabsence of a base.

In a further process, the compounds of the formula I are prepared by aprocedure which comprises reacting a sulfonamide of the formula II givenabove with an isocyanate or isothiocyanate of the formula VI ##STR7## inwhich E, R₃, R₄ and Z are as defined under formula I, in the presence orabsence of a base.

Finally, the compounds of the formula I can also be obtained by aprocedure which comprises reacting an N-phenylsulfonylcarbamate of theformula VII ##STR8## in which A, R₁, R₂, m and X are as defined underformula I and R₁₁ is hydrogen, halogen, nitro or C₁ -C₃ -alkyl, with anamine of the formula V defined above.

If desired, the resulting ureas of the formula I can be converted intoaddition salts by means of amines, alkali metal or alkaline earth metalhydroxides or quaternary ammonium bases. This is effected, for example,by reaction with an equimolar amount of base and evaporation of thesolvent.

The starting materials of the formulae II, IV and VII and theortho-substituted hydroxyphenyl- or substitutedortho-hydroxyphenyl-sulfonamides of the formula VIII ##STR9## in whichR₁ and R₂ are as defined under formula I and X' is oxygen or sulfur, asstarting materials of certain sulfonamide representatives of the formulaII, have been disclosed in European Patent Application 44,807.

Some of the starting materials of the formulae III, V and VI are known.Novel compounds of the formulae III and VI can be obtained byconventional methods from corresponding compounds of the formula V.

Novel fluoroalkoxy-amino-pyrimidines and -triazines of the formula V,their preparation and the preparation of corresponding compounds of theformulae III and VI therefrom have been disclosed in Swiss PatentApplication 3527/82-8.

The reactions to give compounds of the formula I are advantageouslycarried out in aprotic, inert, organic solvents, such as methylenechloride, tetrahydrofuran, acetonitrile, dioxane and toluene. Baseswhich can be used are inorganic bases, such as amines, for exampletriethylamine, quinuclidine, quinoline, pyridine and the like, andinorganic bases, such as hydrides, for example sodium hydride or calciumhydride, hydroxides, for example sodium hydroxide and potassiumhydroxide, carbonates, for example sodium carbonate and potassiumcarbonate, and bicarbonates, for example potassium bicarbonate andsodium bicarbonate.

The reaction temperatures are preferably between -20° and +120° C. Thereactions generally proceed slightly exothermically, and can be carriedout at room temperature. For the purpose of shortening the reaction timeor for initiating the reaction, the mixture is appropriately warmed toits boiling point for a short time.

The end products can be isolated by concentrating the mixture and/orevaporating off the solvent and can be purified by recrystallisation ortrituration of the solid residue in solvents in which they are notreadily soluble, such as ethers, aromatic hydrocarbons and chlorinatedhydrocarbons.

The active substances of the formula I are stable compounds. Theirhandling requires no precautionary measures.

When used in relatively small amounts, the compounds of the formula Ihave good selectively growth-inhibiting and selectively herbicidalproperties which make them excellent for use in crops of useful plants,in particular cereals, cotton, soybean, maize and rice. In some cases,weeds which have hitherto been affected only by total herbicides arealso damaged.

The mode of action of these active substances is unusual. Many of themare translocatable, i.e. they are taken up by the plant and transportedto other points, where they then act. It is thus possible, for example,to damage perennial weeds as far as the roots by surface treatment. Incontrast to other herbicides and growth regulators, the novel compoundsof the formula I already act when applied in very small amounts.

The compounds of the formula I also have powerful plant growthregulating properties, which can result in an increase in the yield ofcrops or harvest. Moreover, many compounds of the formula I exhibit aconcentration-dependent plant growth inhibiting action. The growth ofboth monocotyledons and dicotyledons is impaired.

Thus, for example, the growth of leguminosae frequently planted as covercrops in agriculture in tropical regions can be selectively inhibited bythe compounds of the formula I, so that although soil erosion betweencrops is prevented, the cover crops cannot compete with the crop.

Inhibition of the vegetative growth enables many crop plants to beplanted closer together, so that an increased yield in relation to soilarea can be achieved.

A further mechanism of increasing yield with growth inhibitors is basedon the fact that a greater amount of nutrients is available for flowerand fruit formation, whilst vegetative growth is restricted.

The compounds of the formula I can also be used to prevent storedpotatoes from sprouting. When potatoes are stored over winter, sproutsfrequently develop, resulting in shrinkage, loss of weight and rotting.

When relatively large amounts are applied, the development of all thetested plants is damaged to the extent that the plants die.

The invention also relates to herbicidal and plant growth regulatingcompositions containing a novel active substance of the formula I, andto methods of pre-emergence and post-emergence control of weeds, ofinhibiting the plant growth of monocotyledons and dicotyledons,especially grasses, tropical cover crops and tobacco side-shoots, and ofregulating plant growth, especially of leguminosae.

The compounds of the formula I are used in unmodified form or,preferably, as compositions together with the assistants conventionallyused in the art of formulation, and are therefore processed in a knownmanner to, for example, emulsion concentrates, solutions which can besprayed directly or diluted, dilute emulsions, wettable powders, solublepowders, dusts, granules or compositions encapsulated in, for example,polymeric substances. The methods of application, such as spraying,misting, dusting, scattering or watering, like the type of composition,are chosen according to the intended aims and the given circumstances.

The formulations, i.e. the compositions, preparations or combinationscontaining the active substance of the formula I and, where relevant, asolid or liquid adjuvant are prepared in a known manner, for example byintimate mixing and/or grinding of the active substances with extenders,for example with solvents, solid carriers and, where appropriate,surface-active compounds (surfactants).

Suitable solvents include aromatic hydrocarbons, preferably C₈ -C₁₂-fractions, for example xylene mixtures or substituted naphthalenes,phthalates, such as dibutyl phthalate or dioctyl phthalate, aliphatichydrocarbons, such as cyclohexane or paraffins, alcohols and glycols andethers and esters thereof, such as ethanol, ethylene glycol, ethyleneglycol monomethyl ether or ethylene glycol monoethyl ether, ketones,such as cyclohexanone, highly polar solvents, such asN-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide,vegetable oils, which may be epoxidised, such as epoxidised coconut oilor soybean oil, and water.

Solid carriers used, for example for dusts and dispersible powders, areas a rule ground natural minerals, such as calcite, talc, kaolin,montmorillonite or attapulgite. Highly disperse silica or highlydisperse absorbent polymers can also be added to improve the physicalproperties. Suitable granular, adsorbent carriers include porousmaterials, for example pumice, brick dust, sepiolite or bentonite, andexamples of non-absorptive carriers include calcite and sand. Inaddition, a large number of pregranulated materials of inorganic ororganic nature, such as, in particular, dolomite or comminuted plantresidues, can be used.

Suitable surface-active compounds depend on the nature of the activesubstance of the formula I to be formulated and include non-ionic,cationic and/or anionic surfactants with good emulsifying, dispersingand wetting properties. Surfactants are also to be understood as meaningsurfactant mixtures.

Suitable anionic surfactants can be either so-called water-soluble soapsor water-soluble synthetic surface-active compounds.

Soaps are the alkali metal, alkaline earth metal or substituted orunsubstituted ammonium salts of higher fatty acids (C₁₀ -C₂₂), forexample the Na or K salts of oleic acid or stearic acid, or of naturallyoccurring fatty acid mixtures, which can be isolated, for example, fromcoconut oil or tallow oil. Fatty acid methyl-taurine salts can also beused.

However, so-called synthetic surfactants are more frequently used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylaryl sulfonates.

The fatty sulfonates and sulfates are as a rule in the form of alkalimetal, alkaline earth metal or substituted or unsubstituted ammoniumsalts and contain an alkyl radical having 8 to 22 C atoms, alkyl alsoincluding the alkyl moiety of acyl radicals, for example the Na or Casalt of lignin-sulfonic acid, of dodecyl-sulfuric acid ester or of afatty alcohol sulfate mixture prepared from naturally occurring fattyacids. These also include the salts of sulfuric acid esters and sulfonicacids of fatty alcohol/ethylene oxide adducts. The sulfonatedbenzimidazole derivatives preferably contain 2 sulfonic acid groups anda fatty acid radical having 8-22 C atoms. Examples of alkylarylsulfonates are the Na, Ca or triethanolamine salts ofdodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or anaphthalenesulfonic acid/formaldehyde condensate.

Corresponding phosphates, for example salts of the phosphoric acid esterof a p-nonylphenol/ethylene oxide 4:14 adduct, can also be used.

Suitable non-ionic surfactants include, in particular, polyglycol etherderivatives of aliphatic or cycloaliphtic alcohols, saturated orunsaturated fatty acids and alkylphenols, which can contain 3 to 30glycol ether groups and 8 to 20 carbon atoms in the (aliphatic)hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of thealkylphenols.

Other suitable non-ionic surfactants are the watersoluble adducts,containing 20 to 250 ethylene glycol ether groups and 10 to 100propylene glycol ether groups, of polyethylene oxide and polypropyleneglycol, ethylenediaminopolypropylene glycol and an alkylpolypropyleneglycol having 1 to 10 carbon atoms in the alkyl chain. The abovecompounds usually contain 1 to 5 ethylene glycol units per propyleneglycol unit.

Examples of non-ionic surfactants includenonylphenol-polyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts, tributylphenoxypolyethanol,polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylenesorbitan trioleate, can also be used.

The cationic surfactants are, in particular, quaternary ammonium saltswhich contain at least one alkyl radical having 8 to 22 C atoms as anN-substituent and, as further substituents, lower alkyl radicals, whichmay be halogenated, benzyl or lower hydroxyalkyl radicals. The salts arepreferably in the form of halides, methyl-sulfates or ethylsulfates, forexample stearyltrimethylammonium chloride andbenzyldi-(2-chloroethyl)-ethylammonium bromide.

The surfactants customary in the art of formulation are described in,inter alia, the following publications: "McCutcheon's Detergents andEmulsifiers Annual" MC Publishing Corp., Ridgewood, N.J., 1979 andSisley and Wood, "Encyclopedia of Surface Active Agents". ChemicalPublishing Co., Inc. New York, 1964.

The pesticidal preparations as a rule contain 0.1 to 95%, in particular0.1 to 80%, of active substance of the formula I, 1 to 99.9% of a solidor liquid adjuvant and 0 to 25%, in particular 0.1 to 25%, of asurfactant.

In particular, preferred formulations have the following compositions:(%=percent by weight)

    ______________________________________                                        Emulsifiable                                                                  concentrates                                                                  Active substance:                                                                           1 to 20%,  preferably 5 to 10%                                  Surfactant:   5 to 30%,  preferably 10 to 20%                                 Liquid carrier:                                                                             50 to 94%, preferably 70 to 85%.                                Dusts                                                                         Active substance:                                                                           0.1 to 10%,                                                                              preferably 0.1 to 1%                                 Solid carrier:                                                                              99.9 to 90%,                                                                             preferably 99.9 to 99%.                              Suspension concentrates                                                       Active substance:                                                                           5 to 75%,  preferably 10 to 50%                                 Water:        94 to 25%, preferably 90 to 30%                                 Surfactant:   1 to 40%,  preferably 2 to 30%.                                 Wettable powders                                                              Active substance:                                                                           0.5 to 90%,                                                                              preferably 1 to 80%                                  Surfactant:   0.5 to 20%,                                                                              preferably 1 to 15%                                  Solid carrier:                                                                              5 to 95%,  preferably 15 to 90%.                                Granules                                                                      Active substance:                                                                           0.5 to 30%,                                                                              preferably 3 to 15%                                  Solid carrier:                                                                              99.5 to 70%,                                                                             preferably 97 to 85%.                                ______________________________________                                    

Whilst concentrated compositions are preferred as commercial products,the end consumer as a rule uses dilute compositions. The use forms canbe diluted down to 0.001% of active substance. The amounts applied areas a rule 0.01 to 10 kg of active substance/ha, preferably 0.025 to 5 kgof active substance/ha.

The compositions can also contain other additives such as stabilisers,antifoams, viscosity regulators, binders, tackifiers and fertilisers orother active substances to achieve special effects.

In the following examples, the temperatures are given in degreescentigrade °C. and the pressures are given in millibars mb.

PREPARATION EXAMPLES EXAMPLE 1N-(2-Difluoromethoxyphenyl-sulfonyl)-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]-urea

(a) 124.6 g of 2-difluoromethoxyphenyl-sulfonyl isocyanate in 100 ml ofdioxane are added dropwise to a suspension of 80.3 g of2-amino-4-chloro-6-methoxy-1,3,5-triazine in 400 ml of absolute dioxanein the course of 10 minutes. The reaction mixture is warmed to 90°-100°for 3 hours, and the solution is then cooled and concentrated to give180 g ofN-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-chloro-6-methoxy-1,3,5-triazin-2-yl)-ureaof melting point 167°-168°.

(b) A mixture of 8.2 g ofN-(2-difluoromethoxyphenylsulfonyl)-N'-(4-chloro-6-methoxy-1,3,5-triazin-2-yl)-urea,60 ml of dioxane, 20 ml of 2,2,2-trifluoroethanol and 5.5 g of potassiumcarbonate is stirred at 55°-60° for 12 hours and then taken up in 300 mlof water and filtered over active charcoal. After the mixture has beenacidified with 2 N hydrochloric acid, the product precipitates and isseparated off by filtration. Yield: 7.7 g ofN-(2-difluoromethoxyphenyl-sulfonyl)-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]-ureaof melting point 155°-157°.

EXAMPLE 2N-(2-Difluoromethoxyphenyl-sulfonyl)-N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-urea

(a) Gaseous difluorochloromethane is passed into a solution of 62.5 g of2-amino-4-hydroxy-6-methyl-pyrimidine in 500 ml of water, 100 ml of 40%sodium hydroxide solution and 100 ml of dioxane at a temperature of70°-75° C. over a period of 12 hours. During this period, at hourlyintervals, a total of 160 g of solid sodium hydroxide is added in equalportions. The organic phase is separated off and concentrated to about1/10 of its volume, the residue is poured into water and the solid whichhas precipitated is separated off to give 39.9 g of2-amino-4-difluoromethoxy-6-methyl-pyrimidine of melting point 136°-137°C.

(b) A mixture of 2.5 g of 2-difluoromethoxyphenylsulfonyl isocyanate,1.75 g of 2-amino-4-difluoromethoxy-6-methyl-pyrimidine and 30 ml ofabsolute dioxane is stirred at a temperature of 70°-75° C. for 2 hours.The solution is evaporated and the residue is crystallised from ether togive 4.0 g ofN-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-ureaof melting point 163°-164° C.

EXAMPLE 3N-[2-(2-Ethoxy-ethoxy)-phenyl-sulfonyl]-N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-urea

(a) 3.9 g (0.025 mol) of phenyl chloroformate and 0.05 g of4-dimethylamino-pyridine are added in succession to a solution of 9.0 g(0.05 mol) of 2-amino-4-difluoromethoxy-6-methyl-pyrimidine in 30 ml ofabsolute tetrahydrofuran. The solution is stirred at 20°-25° C. for 24hours and the reaction mixture is then diluted with 250 ml of ethylacetate and the precipitate is separated off. 3.1 g of2-amino-4-difluoromethoxy-6-methyl-pyrimidine hydrochloride of meltingpoint 204°-205° C. (decomposition) are thus obtained. To remove theresidual starting material, the filtrate is eluted over a columncontaining the ion exchanger I® (MERCK), and the eluate is dried oversodium sulfate and evaporated. 4.0 g of2-phenoxycarbonylamino-4-difluoromethoxy-6-methyl-pyrimidine areobtained as the crude product in the form of a viscous oil. Aftercrystallisation, the product has a melting point of 56°-58° C.

¹ H-NMR (CDCl₃): δ=2.5 (s,CH₃), 6.45 (s,1H), 7.0-7.5 (5H), 7.56 (t,J=70Hz, CHF₂) and 9.0 (NH) ppm.

(b) 1.8 g (0.012 mol) of 1,5-diazabicyclo(5.4.0)undec-5-ene are added toa solution of 3.5 g (0.012 mol) of2-phenoxycarbonylamino-4-difluoromethoxy-6-methyl-pyrimidine, in theform of the crude product, and 2.9 g (0.012 mol) of2-(2-ethoxy-ethoxy)-benzenesulfonamide in 100 ml of absoluteacetonitrile and the mixture is stirred at 20°-25° C. for 1 hour andthen diluted with 500 ml of water and acidified with hydrochloric acid.The oil which separates out is taken up in 200 ml of ethyl acetate andthe mixture is dried over sodium sulfate and evaporated. The oilyresidue is crystallised from diethyl ether and acetone to giveN-[2-(2-ethoxyethoxy)-phenyl-sulfonyl]-N'-(4-difluoromethoxy-6-methylpyrimidin-2-yl)-ureaof melting point 90°-95° C. (decomposition) as colourless crystals in ayield of 2.7 g.

EXAMPLE 4 2-Amino-4-difluoromethylthio-6-methoxy-1,3,5-triazine

10.0 g of gaseous difluorochloromethane are passed into a suspension of5.0 g of 2-amino-4-mercapto-6-methoxy-1,3,5-triazine and 4.8 g ofpotassium carbonate in 100 ml of dimethylformamide at a temperature of70°-75° C. over a period of 90 minutes. The reaction mixture isevaporated, the residue is stirred with water and the solid precipitateis separated off to give 1.6 g of2-amino-4-difluoromethylthio-6-methoxy-1,3,5-triazine of melting point146°-150° C.

EXAMPLE 5 2-Amino-4-chloro-6-difluoromethoxy-pyrimidine

A suspension of 16.4 g of 2-amino-4,6-dichloropyrimidine in 100 ml of40% sodium hydroxide solution is stirred at a temperature of 95°-100° C.for 1 hour. 200 ml of dioxane are added, and 20 g of gaseousdifluorochloromethane are passed in at a temperature of 70°-75° C. inthe course of 1 hour. The organic phase is separated off andconcentrated to about 1/5 of its volume, the residue is poured intowater and the solid precipitate is separated off to give 6 g of2-amino-4-chloro-6-difluoromethoxy-pyrimidine of melting point 118°-119°C.

EXAMPLE 6 2-Amino-4-difluoromethoxy-6-methoxy-pyrimidine

19.2 g of 2-amino-4,6-dimethoxy-pyrimidine hydrochloride are heated at150° C. for 2 hours, during which methyl chloride is detached to give2-amino-4-hydroxy-6-methoxy-pyrimidine. 80 ml of 40% sodium hydroxidesolution and 100 ml of dioxane are added, and 22 g ofdifluorochloromethane are passed in at 70°-75° in the course of 3/4 ofan hour. The organic phase is separated off and concentrated to about1/5 of its volume, the residue is poured into water and the solidprecipitate is separated off to give 2.4 g of2-amino-4-difluoromethoxy-6-methoxy-pyrimidine of melting point106°-107° C.

EXAMPLE 72-Amino-4-methyl-6-[1,1,2-trifluoro-2-chloro-ethoxy]-pyrimidine

25 g of 2-amino-4-hydroxy-6-methyl-pyrimidine, 25.6 g ofchlorotrifluoroethylene, 13.8 g of potassium hydroxide and 200 ml ofdimethylformamide are stirred together at 60° in an autoclave for 8hours. The mixture is diluted with water and extracted with ethylacetate and the extract is evaporated to give a dark oil. A littlemethylene chloride is added and the crystalline precipitate formed isseparated off to give 8.7 g of2-amino-4-methyl-6-(1,1,2-trifluoro-2-chloro-ethoxy)-pyrimidine ofmelting point 73°-74° C.

The end products listed in the following table are obtained in a similarmanner.

                                      TABLE 1                                     __________________________________________________________________________     ##STR10##                                                                                                                              Melting                                                                       point               No.                                                                              R.sub.1                                                                            R.sub.2                                                                           X  A              Z E  R.sub.3  R.sub.4       [°C.]        __________________________________________________________________________    1  H    H   O  CHF.sub.2      O N  CH.sub.3 OCH.sub.2CF.sub.3                                                                           110-112°                                                               8                   2  H    H   O  CHF.sub.2      O N  C.sub.2 H.sub.5                                                                        OCH.sub.2CF.sub.3                                                                           129-131°                                                               .                   3  H    H   O  CHF.sub.2      O N  OC.sub.2 H.sub.5                                                                       OCH.sub.2CF.sub.                                                                            147-148°     4  H    H   O  CHF.sub.2      S N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 5  H    H   S  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           152-154°     6  H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           155-157°     7  H    H   O  CF.sub.2CHF.sub.2                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           169-170°     8  H    H   O  CF.sub.3       O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           157-159°     9  H    H   O  CHF.sub.2      O CN OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           164-165°     10 H    H   O  CHF.sub.2      O CH CH.sub.3 OCH.sub.2CF.sub.3                                                                           157-158°     11 H    H   O  CHF.sub.2      O CH Cl       OCH.sub.2CF.sub.3                                                                           147-148°     12 H    H   O  CHF.sub.2      O CH SCH.sub.3                                                                              OCH.sub.2CF.sub.3                 13 H    H   O  CHF.sub.2      O CH CH.sub.2 Cl                                                                            OCH.sub.2CF.sub.3                                                                           114-118°     14 H    H   S  CHF.sub.2      O CH OCH.sub. 3                                                                             OCH.sub.2CF.sub.3                                                                           169-170°     15 H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl                                                                        119-120°     16 H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F                                                                          94-95°      17 H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Br              18 H    H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              19 H    H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F                                                                         88°                                                                    (decom-                                                                       position)           20 5-F  H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           117-119°     21 H    6-Cl                                                                              O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           126-127°     22 5-F  H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 23 5-F  H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl                                                                        141-148°     24 H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 25 H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           135-137°     26 H    H   O  CClCHCl        O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           133-134°     27 H    H   O  CH.sub.2 CH.sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           146-148°     28 H    H   O  CH.sub.2OCH.sub.3                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 29 5-Cl H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 30 5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 31 H    H   O  CHF.sub.2      O CH CH.sub.3 OCHF.sub.2    161-162°     32 H    H   O  CHF.sub.2      O CH CF.sub.3 OCHF.sub.2    130-131°     33 H    H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCHF.sub.2    168-169°     34 H    H   O  CHF.sub.2      O CH Cl       OCHF.sub.2    133-134°     35 H    H   O  CHF.sub.2      O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2    145-146°     36 H    H   O  CHF.sub.2      O CH SCH.sub.3                                                                              OCHF.sub.2                        37 H    H   O  CHF.sub.2      O CH CH.sub.2 F                                                                             OCHF.sub.2                        38 H    H   O  CHF.sub.2      O CH CH.sub.3 SCHF.sub.2                        39 H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              SCHF.sub.2    127-129°     40 H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCHF.sub.2                        41 H    H   O  CHF.sub.2      O N  OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 42 H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               43 H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          44 H    H   O  CHF.sub.2      O N  Cl       OCH.sub.2CF.sub.3                 45 H    H   O  CHF.sub.2      O CH OCH.sub.2CF.sub.3                                                                      OCHF.sub.2                        46 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH CH.sub.3 OCHF.sub.2                        47 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH CF.sub.3 OCHF.sub.2                        48 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH Cl       OCHF.sub.2                        49 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH OCH.sub.3                                                                              OCHF.sub.2                        50 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        51 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH CH.sub.2 F                                                                             OCHF.sub.2                        52 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH SCH.sub.3                                                                              OCHF.sub.2                        53 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH OCH.sub.3                                                                              SCHF.sub.2                        54 H    H   O  CH.sub.2OCH.sub.3                                                                            O N  CH.sub.3 OCHF.sub.2                        55 H    H   O  CH.sub.2OCH.sub.3                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              56 H    H   O  CH.sub.2OCH.sub.3                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               57 H    H   O  CH.sub.2OCH.sub.3                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               58 H    H   O  CH.sub.2OCH.sub.3                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          59 H    H   O  CH.sub.2OCH.sub.3                                                                            O N  CH.sub.3 OCH.sub.2CF.sub.3                 60 H    H   O  CH.sub.2OCH.sub. 3                                                                           O CH CH.sub.3 OCH.sub.2CF.sub.3                 61 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH Cl       OCH.sub.2CF.sub.3                 62 H    H   O  CH.sub.2OCH.sub.3                                                                            O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 63 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCHF.sub.2    180-184°     64 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH CF.sub.3 OCHF.sub.2                        65 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH Cl       OCHF.sub.2                        66 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              OCHF.sub.2                        67 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        68 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.2 F                                                                             OCHF.sub.2                        69 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH SCH.sub.3                                                                              OCHF.sub.2                        70 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              SCHF.sub.2                        71 H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  CH.sub.3 OCHF.sub.2                        72 H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              73 H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               74 H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               75 H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          76 H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  CH.sub.3 OCH.sub.2CF.sub.3                 77 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCH.sub.2CF.sub.3                 78 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH Cl       OCH.sub.2CF.sub.3                 79 H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           190-200°     80 H    H   O  CF.sub.2CF.sub.3                                                                             O CH CH.sub.3 OCHF.sub.2    185-186°     81 H    H   O  CF.sub.2CF.sub.3                                                                             O CH CF.sub.3 OCHF.sub.2                        82 H    H   O  CF.sub.2CF.sub.3                                                                             O CH Cl       OCHF.sub.2                        83 H    H   O  CF.sub.2CF.sub.3                                                                             O CH OCH.sub.3                                                                              OCHF.sub.2                        84 H    H   O  CF.sub.2CF.sub.3                                                                             O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        85 H    H   O  CF.sub.2CF.sub.3                                                                             O CH CH.sub.2 F                                                                             OCHF.sub.2                        86 H    H   O  CF.sub.2CF.sub.3                                                                             O CH SCH.sub.3                                                                              OCHF.sub.2                        87 H    H   O  CF.sub.2CF.sub.3                                                                             O CH OCH.sub.3                                                                              SCHF.sub.2                        88 H    H   O  CF.sub.2CF.sub.2                                                                             O N  CH.sub.3 OCHF.sub.2                        89 H    H   O  CF.sub.2CF.sub.3                                                                             O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              90 H    H   O  CF.sub.2CF.sub.3                                                                             O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               91 H    H   O  CF.sub.2CF.sub.3                                                                             O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               92 H    H   O  CF.sub.2CF.sub.3                                                                             O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          93 H    H   O  CF.sub.2CF.sub.3                                                                             O N  CH.sub.3 OCH.sub.2 CF.sub. 3               94 H    H   O  CF.sub.2CF.sub.3                                                                             O CH CH.sub.3 OCH.sub.2 CF.sub.3                95 H    H   O  CF.sub.2CF.sub.3                                                                             O CH Cl       OCH.sub.2CF.sub.3                 96 H    H   O  CF.sub.2CF.sub.3                                                                             0 CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           166-167°     97 H    H   O  CF.sub.2CF.sub.3                                                                             O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           182-183°     98 H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH CH.sub.3 OCHF.sub.2    148-149°     99 H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH CF.sub.3 OCHF.sub.2                        100                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH Cl       OCHF.sub.2    142-143°     101                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH OCH.sub.3                                                                              OCHF.sub.2    157-158°     102                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH C.sub.2 F.sub.5                                                                        OCHF.sub.2                        103                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH CH.sub.2 F                                                                             OCHF.sub.2                        104                                                                              H    H   O   CH.sub.2CH.sub.2OCH.sub.3                                                                   O CH SCH.sub.3                                                                              OCHF.sub.2                        105                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH OCH.sub.3                                                                              SCHF.sub.2                        106                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O N  CH.sub.3 OCHF.sub.2                        107                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              108                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               109                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               110                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          111                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O N  CH.sub.3 OCH.sub.2CF.sub.3                 112                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH CH.sub.3 OCH.sub.2CF.sub.3                 113                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH Cl       OCH.sub.2CF.sub.3                 114                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 115                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH CH.sub.3 OCHF.sub.2    182-183°     116                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH CF.sub.3 OCHF.sub.2                        117                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH Cl       OCHF.sub.2                        118                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH OCH.sub.3                                                                              OCHF.sub.2                        119                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        120                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH CH.sub.2 F                                                                             OCHF.sub.2                        121                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH SCH.sub.3                                                                              OCHF.sub.2                        122                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH OCH.sub.3                                                                              SCHF.sub.2                        123                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  CH.sub.3 OCHF.sub.2                        124                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              125                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  OCH.sub. 3                                                                             OCH.sub.2CH.sub.2 F               126                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               127                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          128                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  CH.sub.3 OCH.sub.2CF.sub.3                 129                                                                              H    H   O  CH.sub.2CH.sub.3 Cl                                                                          O CH CH.sub.3 OCH.sub.2CF.sub.3                 130                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH Cl       OCH.sub.2CF.sub.3                 131                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 132                                                                              H    H   O  CClCHCl        O CH CH.sub.3 OCHF.sub.2    216-217°                                                               (decom-                                                                       position)           133                                                                              H    H   O  CClCHCl        O CH CF.sub.3 OCHF.sub.2                        134                                                                              H    H   O  CClCHCl        O CH Cl       OCHF.sub.2    195-196°     135                                                                              H    H   O  CClCHCl        O CH OCH.sub.3                                                                              OCHF.sub.2                        136                                                                              H    H   O  CClCHCl        O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        137                                                                              H    H   O  CClCHCl        O CH CH.sub.2 F                                                                             OCHF.sub.2                        138                                                                              H    H   O  CClCHCl        O CH SCH.sub.3                                                                              OCHF.sub.2                        139                                                                              H    H   O  CClCHCl        O CH OCH.sub.3                                                                              SCHF.sub.2                        140                                                                              H    H   O  CClCHCl        O N  CH.sub.3 OCHF.sub.2                        141                                                                              H    H   O  CClCHCl        O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              142                                                                              H    H   O  CClCHCl        O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               143                                                                              H    H   O  CClCHCl        O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               144                                                                              H    H   O  CClCHCl        O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          145                                                                              H    H   O  CClCHCl        O N  CH.sub.3 OCH.sub.2CF.sub.3                 146                                                                              H    H   O  CClCHCl        O CH CH.sub.3 OCH.sub.2CF.sub.3                 147                                                                              H    H   O  CClCHCl        O CH Cl       OCH.sub.2CF.sub.3                 148                                                                              H    H   O  CClCHCl        O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           193-194°     149                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH CH.sub.3 OCHF.sub.2                        150                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH CF.sub.3 OCHF.sub.2                        151                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH Cl       OCHF.sub.2                        152                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH OCH.sub.3                                                                              OCHF.sub.2                        153                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        154                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH CH.sub.2 F                                                                             OCHF.sub.2                        155                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH SCH.sub.3                                                                              OCHF.sub.2                        156                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH OCH.sub.3                                                                              SCHF.sub.2                        157                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O N  CH.sub.3 OCHF.sub.2                        158                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              159                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               160                                                                              H    H   O  CH.sub.2 CF.sub.3                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               161                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          162                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O N  CH.sub.3 OCH.sub.2CF.sub.3                 163                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH CH.sub.3 OCH.sub.2CF.sub.3                 164                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH Cl       OCH.sub.2CF.sub.3                 165                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 166                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 167                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH CH.sub.3 OCHF.sub.2    174-175°     168                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH CF.sub.3 OCHF.sub.2                        169                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH Cl       OCHF.sub.2                        170                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH OCH.sub.3                                                                              OCHF.sub.2                        171                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        172                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH CH.sub.2 F                                                                             OCHF.sub.2                        173                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH SCH.sub.3                                                                              OCHF.sub.2                        174                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH OCH.sub.3                                                                              SCHF.sub.2                        175                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O N  CH.sub.3 OCHF.sub.2                        176                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              177                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               178                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               179                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          180                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O N  CH.sub.3 OCH.sub.2CF.sub.3                 181                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH CH.sub.3 OCH.sub.2CF.sub.3                 182                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH Cl       OCH.sub. 2CF.sub.3                183                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 184                                                                              H    H   O  CF.sub.3       O CH CH.sub.3 OCHF.sub.2    178-179°     185                                                                              H    H   O  CF.sub.3       O CH CF.sub.3 OCHF.sub.2                        186                                                                              H    H   O  CF.sub.3       O CH Cl       OCHF.sub.2    139-141°     187                                                                              H    H   O  CF.sub.3       O CH OCH.sub.3                                                                              OCHF.sub.2    186-187°     188                                                                              H    H   O  CF.sub.3       O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        189                                                                              H    H   O  CF.sub.3       O CH CH.sub.2 F                                                                             OCHF.sub.2                        190                                                                              H    H   O  CF.sub.3       O CH SCH.sub.3                                                                              OCHF.sub.2                        191                                                                              H    H   O  CF.sub.3       O CH OCH.sub.3                                                                              SCHF.sub.2                        192                                                                              H    H   O  CF.sub.3       O N  CH.sub.3 OCHF.sub.2                        193                                                                              H    H   O  CF.sub.3       O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              194                                                                              H    H   O  CF.sub.3       O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               195                                                                              H    H   O  CF.sub.3       O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               196                                                                              H    H   O  CF.sub.3       O N  OCH.sub. 3                                                                             OCH.sub.2CHClCH.sub.2 Cl          197                                                                              H    H   O  CF.sub.3       O N  CH.sub.3 OCH.sub.2CF.sub.3                 198                                                                              H    H   O  CF.sub.3       O CH CH.sub.3 OCH.sub.2CF.sub.3                 199                                                                              H    H   O  CF.sub.3       O CH Cl       OCH.sub.2CF.sub.3                 200                                                                              H    H   O  CF.sub.3       O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 201                                                                              H    H   S  CHF.sub.2      O CH CH.sub.3 OCHF.sub.2    159-160°     __________________________________________________________________________

                                      TABLE 1                                     __________________________________________________________________________     ##STR11##                                                                                                                              Melting                                                                       point               No.                                                                              R.sub.1                                                                            R.sub.2                                                                           X  A              Z E  R.sub.3  R.sub.4       [°C.]        __________________________________________________________________________    202                                                                              H    H   S  CHF.sub.2      O CH CF.sub.3 OCHF.sub.2                        203                                                                              H    H   S  CHF.sub.2      O CH Cl       OCHF.sub.2                        204                                                                              H    H   S  CHF.sub.2      O CH OCH.sub.3                                                                              OCHF.sub.2    144-146°     205                                                                              H    H   S  CHF.sub.2      O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        206                                                                              H    H   S  CHF.sub.2      O CH CH.sub.2 F                                                                             OCHF.sub.2                        207                                                                              H    H   S  CHF.sub.2      O CH SCH.sub.3                                                                              OCHF.sub.2                        208                                                                              H    H   S  CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        209                                                                              H    H   S  CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        210                                                                              H    H   S  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              211                                                                              H    H   S  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               212                                                                              H    H   S  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               213                                                                              H    H   S  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          214                                                                              H    H   S  CHF.sub.2      O N  CH.sub.3 OCH.sub.2CF.sub.3                 215                                                                              H    H   S  CHF.sub.2      O CH CH.sub.3 OCH.sub.2CF.sub.3                 216                                                                              H    H   S  CHF.sub.2      O CH Cl       OCH.sub.2CF.sub.3                 217                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH CH.sub.3 OCHF.sub.2    184-186°     218                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH CF.sub.3 OCHF.sub.2                        219                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH Cl       OCHF.sub.2                        220                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH OCH.sub.3                                                                              OCHF.sub.2                        221                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        222                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH CH.sub.2 F                                                                             OCHF.sub.2                        223                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH SCH.sub.3                                                                              OCHF.sub.2                        224                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        225                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        226                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              227                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               228                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               229                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          230                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O N  CH.sub.3 OCH.sub.2CF.sub.3                 231                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH CH.sub.3 OCH.sub.2CF.sub.3                 232                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH Cl       O CH.sub.2CF.sub.3                233                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 234                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 235                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCHF.sub.2                        236                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH CF.sub.3 OCHF.sub.2                        237                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH Cl       OCHF.sub.2                        238                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              OCHF.sub.2                        239                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        240                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.2 F                                                                             OCHF.sub.2                        241                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH SCH.sub.3                                                                              OCHF.sub.2                        242                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              SCHF.sub.2                        243                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O N  CH.sub.3 OCHF.sub.2                        244                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              O CH.sub.2CH.sub.2 Cl             245                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               246                                                                              5-F  H   O  CH.sub.2CH CH.sub.2                                                                          O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               247                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          248                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O N  CH.sub.3 OCH.sub.2CF.sub.3                 249                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCH.sub.2CF.sub.3                 250                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH Cl       OCH.sub.2CF.sub.3                 251                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 252                                                                              5-F  H   O  CHF.sub.2      O CH CH.sub.3 OCHF.sub.2    150-151°     253                                                                              5-F  H   O  CHF.sub.2      O CH CF.sub.3 OCHF.sub.2                        254                                                                              5-F  H   O  CHF.sub.2      O CH Cl       OCHF.sub.2                        255                                                                              5-F  H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCHF.sub.2                        256                                                                              5-F  H   O  CHF.sub.2      O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        257                                                                              5-F  H   O  CHF.sub.2      O CH CH.sub.2 F                                                                             OCHF.sub.2                        258                                                                              5-F  H   O  CHF.sub.2      O CH SCH.sub.3                                                                              OCHF.sub.2                        259                                                                              5-F  H   O  CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        260                                                                              5-F  H   O  CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        261                                                                              5-F  H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              262                                                                              5-F  H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               263                                                                              5-F  H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               264                                                                              5-F  H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          265                                                                              5-F  H   O  CHF.sub.2      O N  CH.sub.3 OCH.sub.2CF.sub.3                 266                                                                              5-F  H   O  CHF.sub.2      O CH CH.sub.3 OCH.sub.2CF.sub.3                 267                                                                              5-F  H   O  CHF.sub.2      O CH Cl       OCH.sub.2CF.sub.3                 268                                                                              5-F  H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 269                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH CH.sub.3 OCHF.sub.2    103-104°     270                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH CF.sub.3 OCHF.sub.2                        271                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH Cl       OCHF.sub.2                        272                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH OCH.sub.3                                                                              OCHF.sub.2    112-114°     273                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH C.sub.2 H.sub.5                                                                        OCHF.sub.2                        274                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH CH.sub.2 F                                                                             OCHF.sub.2                        275                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH SCH.sub.3                                                                              OCHF.sub.2                        276                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        277                                                                              H    6-Cl                                                                              O  CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        278                                                                              H    6-Cl                                                                              O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 Cl              279                                                                              H    6-Cl                                                                              O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CH.sub.2 F               280                                                                              H    6-Cl                                                                              O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHCl.sub.2               281                                                                              H    6-Cl                                                                              O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CHClCH.sub.2 Cl          282                                                                              H    6-Cl                                                                              O  CHF.sub.2      O N  CH.sub.3 OCH.sub.2CF.sub.3                 283                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH CH.sub.3 OCH.sub.2CF.sub.3                 284                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH Cl       OCH.sub.2CF.sub.3                 285                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 286                                                                              H    H   O  CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                             O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           136-138°     287                                                                              H    H   O  CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                             O CH OCH.sub.3                                                                              OCHF.sub.2                        288                                                                              H    H   O  CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                             O CH CH.sub.3 OCHF.sub.2    138-140°     289                                                                              H    H   O  CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                             O CH Cl       OCHF.sub.2                        290                                                                              H    H   O  CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                             O CH CH.sub.3 OCH.sub.2CF.sub.3                 291                                                                              H    H   O  CF.sub.2CHFCl  O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           173-174°     292                                                                              H    H   O  CF.sub.2CHFCl  O CH OCH.sub.3                                                                              OCHF.sub.2                        293                                                                              H    H   O  CF.sub.2CHFCl  O CH CH.sub.3 OCHF.sub. 2   157-158°     294                                                                              H    H   O  CF.sub.2CHFCl  O CH Cl       OCHF.sub.2                        295                                                                              H    H   O  CF.sub.2CHFCl  O CH CH.sub.3 OCH.sub.2CF.sub.3                 296                                                                              H    H   O  CH.sub.2C(CH.sub.3)CH.sub.2                                                                  O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 297                                                                              H    H   O  CH.sub.2C(CH.sub.3)CH.sub.2                                                                  O CH OCH.sub.3                                                                              OCHF.sub.2                        298                                                                              H    H   O  CH.sub.2C(CH.sub.3)CH.sub.2                                                                  O CH CH.sub.3 OCHF.sub.2    149-151°     299                                                                              H    H   O  CH.sub.2C(CH.sub.3)CH.sub.2                                                                  O CH Cl       OCHF.sub.2                        300                                                                              H    H   O  CH.sub.2C(CH.sub.3)CH.sub.2                                                                  O CH CH.sub.3 OCH.sub.2CF.sub.3                 301                                                                              H    H   O  CH.sub.2C(CH.sub.3)CH.sub.2                                                                  O CH OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           218-219°     302                                                                              H    H   O  CH.sub.2CHClCH.sub.2 Cl                                                                      O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 303                                                                              H    H   O  CH.sub.2CHClCH.sub.2 Cl                                                                      O CH OCH.sub.3                                                                              OCHF.sub.2                        304                                                                              H    H   O  CH.sub.2CHClCH.sub.2 Cl                                                                      O CH CH.sub.3 OCHF.sub.2                        305                                                                              H    H   O  CH.sub.2CHClCH.sub.2 Cl                                                                      O CH CL       OCHF.sub.2                        306                                                                              H    H   O  CH.sub.2CHClCH.sub.2 Cl                                                                      O CH CH.sub.3 OCH.sub.2CF.sub.3                 307                                                                              H    H   O  CH(CH.sub.2 Cl).sub.2                                                                        O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 308                                                                              H    H   O  CH(CH.sub.2 Cl).sub.2                                                                        O CH OCH.sub.3                                                                              OCHF.sub.2                        309                                                                              H    H   O  CH(CH.sub.2 Cl).sub.2                                                                        O CH CH.sub.3 OCHF.sub.2                        310                                                                              H    H   O  CH(CH.sub.2 Cl).sub.2                                                                        O CH Cl       OCHF.sub.2                        311                                                                              H    H   O  CH(CH.sub.2 Cl).sub.2                                                                        O CH CH.sub.3 OCH.sub.2CF.sub.3                 312                                                                              H    H   O  CH.sub.2CHC(CH.sub.3).sub.2                                                                  O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 313                                                                              H    H   O  CH.sub.2CHC(CH.sub.3).sub.2                                                                  O CH OCH.sub.3                                                                              OCHF.sub.2                        314                                                                              H    H   O  CH.sub.2CHC(CH.sub.3).sub.2                                                                  O CH CH.sub.3 OCHF.sub.2                        315                                                                              H    H   O  CH.sub.2CH C(CH.sub.3).sub.2                                                                 O CH Cl       OCHF.sub.2                        316                                                                              H    H   O  CH.sub.2CHC(CH.sub.3).sub.2                                                                  O CH CH.sub.3 OCH.sub.2CF.sub.3                 317                                                                              H    H   O  CH.sub.2CH.sub.2 F                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 318                                                                              H    H   O  CH.sub.2CH.sub.2 F                                                                           O CH OCH.sub.3                                                                              OCHF.sub.2                        319                                                                              H    H   O  CH.sub.2CH.sub.2 F                                                                           O CH CH.sub.3 OCHF.sub.2                        320                                                                              H    H   O  CH.sub.2CH.sub.2 F                                                                           O CH Cl       OCHF.sub.2                        321                                                                              H    H   O  CH.sub.2CH.sub.2 F                                                                           O CH CH.sub.3 OCH.sub.2CF.sub.3                 322                                                                              H    H   O  CH.sub.2CHCl.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 323                                                                              H    H   O  CH.sub.2CHCl.sub.2                                                                           O CH OCH.sub.3                                                                              OCHF.sub.2                        324                                                                              H    H   O  CH.sub.2CHCl.sub.2                                                                           O CH CH.sub.3 OCHF.sub.2                        325                                                                              H    H   O  CH.sub.2CHCl.sub.2                                                                           O CH Cl       OCHF.sub.2                        326                                                                              H    H   O  CH.sub.2CHCl.sub.2                                                                           O CH CH.sub.3 OCH.sub.2CF.sub.3                 327                                                                              H    H   O  CH.sub.2CCl.sub.3                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 328                                                                              H    H   O  CH.sub.2CCl.sub.3                                                                            O CH OCH.sub.3                                                                              OCHF.sub.2                        329                                                                              H    H   O  CH.sub.2CCl.sub.3                                                                            O CH CH.sub.3 OCHF.sub.2                        330                                                                              H    H   O  CH.sub.2CCl.sub.3                                                                            O CH Cl       OCHF.sub.2                        331                                                                              H    H   O  CH.sub.2CCl.sub.3                                                                            O CH CH.sub.3 OCH.sub.2CF.sub.3                 332                                                                              H    H   S  CF.sub.2CHF.sub.2                                                                            O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 333                                                                              H    H   S  CF.sub.2CHF.sub.2                                                                            O CH OCH.sub.3                                                                              OCHF.sub.2                        334                                                                              H    H   S  CF.sub.2CHF.sub.2                                                                            O CH CH.sub.3 OCHF.sub.2                        335                                                                              H    H   S  CF.sub.2CHF.sub.2                                                                            O CH Cl       OCHF.sub.2                        336                                                                              H    H   S  CF.sub.2CHF.sub.2                                                                            O CH CH.sub.3 OCH.sub.2CF.sub.3                 337                                                                              H    H   O  CH.sub.2CHCHCH.sub.3                                                                         O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           148-153°     338                                                                              H    H   O  CH.sub.2CHCHCH.sub.3                                                                         O CH OCH.sub.3                                                                              OCHF.sub.2                        339                                                                              H    H   O  CH.sub.2CHCHCH.sub.3                                                                         O CH CH.sub.3 OCHF.sub.2    171-172°     340                                                                              H    H   O  CH.sub.2CHCHCH.sub.3                                                                         O CH Cl       OCHF.sub.2                        341                                                                              H    H   O  CH.sub.2CHCHCH.sub.3                                                                         O CH CH.sub.3 OCH.sub.2CF.sub.3                 342                                                                              H    H   O  CH.sub.2CHClCHClCH.sub.3                                                                     O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 343                                                                              H    H   O  CH.sub.2CHClCHClCH.sub.3                                                                     O CH OCH.sub.3                                                                              OCHF.sub.2                        344                                                                              H    H   O  CH.sub.2CHClCHClCH.sub.3                                                                     O CH CH.sub.3 OCHF.sub.2                        345                                                                              H    H   O  CH.sub.2CHClCHClCH.sub.3                                                                     O CH Cl       OCHF.sub.2                        346                                                                              H    H   O  CH.sub.2CHClCHClCH.sub.3                                                                     O CH CH.sub.3 OCH.sub.2CF.sub.3                 347                                                                              H    H   O  CF.sub.2 Cl    O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 348                                                                              H    H   O  CF.sub.2 Cl    O CH OCH.sub.3                                                                              OCHF.sub.2                        349                                                                              H    H   O  CF.sub.2 Cl    O CH CH.sub.3 OCHF.sub.2                        350                                                                              H    H   O  CF.sub.2 Cl    O CH Cl       OCHF.sub.2                        351                                                                              H    H   O  CF.sub.2 Cl    O CH CH.sub.3 OCH.sub.2CF.sub.3                 352                                                                              H    H   O  CF.sub.2 Br    O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 353                                                                              H    H   O  CF.sub.2 Br    O CH OCH.sub.3                                                                              OCHF.sub.2                        354                                                                              H    H   O  CF.sub.2 Br    O CH CH.sub.3 OCHF.sub.2                        355                                                                              H    H   O  CF.sub.2 Br    O CH Cl       OCHF.sub.2                        356                                                                              H    H   O  CF.sub.2 Br    O CH CH.sub.3 OCH.sub.2CF.sub.3                 357                                                                              5-Cl H   O  OCHF.sub.2     O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           92-94°       358                                                                              5-Cl H   O  OCHF.sub.2     O CH OCH.sub.3                                                                              OCHF.sub.2                        359                                                                              5-Cl H   O  OCHF.sub.2     O CH CH.sub.3 OCHF.sub.2    133-134°     360                                                                              5-Cl H   O  OCHF.sub.2     O CH Cl       OCHF.sub.2                        361                                                                              5-Cl H   O  OCHF.sub.2     O CH CH.sub.3 OCH.sub.2CF.sub.3                                                                           153--155°    362                                                                              H    6-F O  CHF.sub.2      O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 363                                                                              H    6-F O  CHF.sub.2      O CH OCH.sub.3                                                                              OCHF.sub.2                        364                                                                              H    6-F O  CHF.sub.2      O CH CH.sub.3 OCHF.sub.2                        365                                                                              H    6-F O  CHF.sub.2      O CH CH       OCHF.sub.2                        366                                                                              H    6-F O  CHF.sub.2      O CH CH.sub.3 OCH.sub.2CF.sub.3                 367                                                                              5-OCH.sub.3                                                                        H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 368                                                                              5-OCH.sub.3                                                                        H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              OCHF.sub.2                        369                                                                              5-OCH.sub.3                                                                        H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCHF.sub.2                        370                                                                              5-OCH.sub.3                                                                        H   O  CH.sub.2CHCH.sub.2                                                                           O CH Cl       OCHF.sub.2                        371                                                                              5-OCH.sub.3                                                                        H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCH.sub.2CF.sub.3                 372                                                                              H    3-CH.sub.3                                                                        O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 373                                                                              H    3-CH.sub.3                                                                        O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              OCHF.sub.2                        374                                                                              H    3-CH.sub.3                                                                        O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCHF.sub.2                        375                                                                              H    3-CH.sub.3                                                                        O  CH.sub.2CHCH.sub.2                                                                           O CH Cl       OCHF.sub.2                        376                                                                              H    3-CH.sub.3                                                                        O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCH.sub.2CF.sub.3                 377                                                                              H    H   O  CH.sub.2C(CH.sub.3)ClCH.sub.2Cl                                                              O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 378                                                                              H    H   O  CH.sub.2C(CH.sub.3)ClCH.sub.2Cl                                                              O CH OCH.sub.3                                                                              OCHF.sub.2                        379                                                                              H    H   O  CH.sub.2C(CH.sub.3)ClCH.sub.2Cl                                                              O CH CH.sub.3 OCHF.sub.2                        380                                                                              H    H   O  CH.sub.2C(CH.sub.3)ClCH.sub.2Cl                                                              O CH Cl       OCHF.sub.2                        381                                                                              H    H   O  CH.sub.2C(CH.sub.3)ClCH.sub.2Cl                                                              O CH CH.sub.3 OCH.sub.2CF.sub.3                 382                                                                              H    H   O  CH.sub.2CHCl.sub.2                                                                           O N  CH.sub.3 OCHF.sub.2                        383                                                                              H    H   O  CH.sub.2CCl.sub.3                                                                            O N  CH.sub.3 OCHF.sub.2                        384                                                                              H    H   O  CF.sub.2 Cl    O N  CH.sub.3 OCHF.sub.2                        385                                                                              H    H   O  CF.sub.2 Br    O N  CH.sub.3 OCHF.sub.2                        386                                                                              H    H   S  CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        387                                                                              H    H   S  CF.sub.2CHF.sub.2                                                                            O N  CH.sub.3 OCHF.sub.2                        388                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        389                                                                              5-F  H   O  CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        390                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O N  CH.sub.3 OCHF.sub.2                        391                                                                              H    6-Cl                                                                              O  CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        392                                                                              5-Cl H   O  CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        393                                                                              H    6-F O  CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        394                                                                              5-OCH.sub.3                                                                        H   O  CH.sub.2 CHCH.sub.2                                                                          O N  CH.sub.3 OCHF.sub.2                        395                                                                              H    3-CH.sub.3                                                                        O  CH.sub.2 CHCH.sub.2                                                                          O N  CH.sub.3 OCHF.sub.2                        396                                                                              H    H   O  CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                             O N  CH.sub.3 OCHF.sub.2                        397                                                                              H    H   O  CH.sub.2CC(CH.sub.3).sub.2                                                                   O N  CH.sub.3 OCHF.sub.2                        398                                                                              H    H   O  CHF.sub.2      O N  CH.sub.3 OCHF.sub.2                        399                                                                              H    H   O  CF.sub.3       O N  CH.sub.3 OCHF.sub.2                        400                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O N  CH.sub.3 OCHF.sub.2                        401                                                                              H    H   O  CH.sub.2CF.sub. 3                                                                            O N  CH.sub.3 OCHF.sub.2                        402                                                                              H    H   O  CClCHCl        O N  CH.sub.3 OCHF.sub.2                        403                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  CH.sub.3 OCHF.sub.2                        404                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O N  CH.sub.3 OCHF.sub.2                        405                                                                              H    H   O  CF.sub.2CF.sub.3                                                                             O N  CH.sub.3 OCHF.sub.2                        406                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  CH.sub.3 OCHF.sub.2                        407                                                                              H    H   O  CH.sub.2OCH.sub.3                                                                            O N  CH.sub.3 OCHF.sub.2                        408                                                                              H    H   O  CF.sub.2CHClF  O N  CH.sub.3 OCHF.sub.2                        409                                                                              H    H   O  CH.sub.2CHCHCH.sub.3                                                                         O N  CH.sub.3 OCHF.sub.2                        410                                                                              H    H   O  CH.sub.2CHClCH.sub.2 Cl                                                                      O N  CH.sub.3 OCHF.sub.2                        411                                                                              H    H   O  CH(CH.sub.2 Cl).sub.2                                                                        O N  CH.sub.3 OCHF.sub.2                        412                                                                              H    H   O  CH.sub.2CH.sub.2 F                                                                           O N  CH.sub.3 OCHF.sub.2                        413                                                                              H    H   O  CH.sub.2C(CH.sub.3)CH.sub.2                                                                  O N  CH.sub.3 OCHF.sub.2                        414                                                                              H    H   O  CHF.sub.2      S N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 415                                                                              H    H   O  CHF.sub.2      S CH CH.sub.3 OCHF.sub.2    174-175°                                                               (decom-                                                                       position)           416                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           S N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 417                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           S CH CH.sub.3 OCHF.sub.2                        418                                                                              H    H   O  CF.sub.3       S N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 419                                                                              H    H   O  CF.sub.3       S CH CH.sub.3 OCHF.sub.2                        420                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    S N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 __________________________________________________________________________

                                      TABLE 1                                     __________________________________________________________________________     ##STR12##                                                                                                                              Melting                                                                       point               No.                                                                              R.sub.1                                                                            R.sub.2                                                                           X  A              Z E  R.sub.3  R.sub.4       [°C.]        __________________________________________________________________________    421                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    S CH CH.sub.3 OCHF.sub.2                        422                                                                              H    H   O  CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2    120-121°     423                                                                              H    H   O  CF.sub.3       O CH OCH.sub.3                                                                              SCHF.sub.2                        424                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH OCH.sub.3                                                                              SCHF.sub.2                        425                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH OCH.sub.3                                                                              SCHF.sub.2                        426                                                                              H    H   O  CClCHCl        O CH OCH.sub.3                                                                              SCHF.sub.2                        427                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH OCH.sub.3                                                                              SCHF.sub.2                        428                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH OCH.sub.3                                                                              SCHF.sub.2                        429                                                                              H    H   O  CF.sub.2CF.sub.3                                                                             O CH OCH.sub.3                                                                              SCHF.sub.2                        430                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              SCHF.sub.2                        431                                                                              H    H   O  CH.sub.2OCH.sub.3                                                                            O CH OCH.sub.3                                                                              SCHF.sub.2                        432                                                                              H    H   O  CF.sub.2CHClF  O CH OCH.sub.3                                                                              SCHF.sub.2                        433                                                                              H    H   O  CH.sub.2CHCHCH.sub.3                                                                         O CH OCH.sub.3                                                                              SCHF.sub.2                        434                                                                              H    H   O  CH.sub.2CHClCH.sub.2 Cl                                                                      O CH OCH.sub.3                                                                              SCHF.sub.2                        435                                                                              H    H   O  CH(CH.sub.2 Cl).sub.2                                                                        O CH OCH.sub.3                                                                              SCHF.sub.2                        436                                                                              H    H   O  CH.sub.2CH.sub.2 F                                                                           O CH OCH.sub.3                                                                              SCHF.sub.2                        437                                                                              H    H   O  CH.sub.2C(CH.sub.3 )CH.sub.2                                                                 O CH OCH.sub.3                                                                              SCHF.sub.2                        438                                                                              H    H   O  CH.sub.2CHCl.sub.2                                                                           O CH OCH.sub.3                                                                              SCHF.sub.2                        439                                                                              H    H   O  CH.sub.2CCl.sub.3                                                                            O CH OCH.sub.3                                                                              SCHF.sub.2                        440                                                                              H    H   O  CF.sub.2 Cl    O CH OCH.sub.3                                                                              SCHF.sub.2                        441                                                                              H    H   O  CF.sub.2 Br    O CH OCH.sub.3                                                                              SCHF.sub.2                        442                                                                              H    H   S  CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        443                                                                              H    H   S  CF.sub.2CHF.sub.2                                                                            O CH OCH.sub.3                                                                              SCHF.sub.2                        444                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        445                                                                              5-F  H   O  CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        446                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              SCHF.sub.2                        447                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        448                                                                              5-Cl H   O  CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        449                                                                              H    6-F O  CHF.sub.2      O CH OCH.sub.3                                                                              SCHF.sub.2                        450                                                                              5-OCH.sub.3                                                                        H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              SCHF.sub.2                        451                                                                              H    3-CH.sub.3                                                                        O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub. 3                                                                             SCHF.sub.2                        452                                                                              H    H   O  CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                             O CH OCH.sub.3                                                                              SCHF.sub.2                        453                                                                              H    H   O  CH.sub.2CC(CH.sub.3).sub.2                                                                   O CH OCH.sub.3                                                                              SCHF.sub.2                        454                                                                              H    H   O  CHF.sub.2      O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                                                                           165-166°     455                                                                              H    H   O  CF.sub.3       O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 456                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 457                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 458                                                                              H    H   O  CClCHCl        O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 459                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 460                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 461                                                                              H    H   O  CF.sub.2CF.sub.3                                                                             O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 462                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 463                                                                              H    H   O  CH.sub.2OCH.sub.3                                                                            O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 464                                                                              H    H   O  CF.sub.2CHClF  O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 465                                                                              H    H   O  CH.sub.2CHCHCH.sub.3                                                                         O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 466                                                                              H    H   O  CH.sub.2CHClCH.sub.2 Cl                                                                      O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 467                                                                              H    H   O  CH(CH.sub.2 Cl).sub.2                                                                        O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 468                                                                              H    H   O  CH.sub.2CH.sub.2 F                                                                           O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 469                                                                              H    H   O  CH.sub.2C(CH.sub.3) CH.sub.2                                                                 O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 470                                                                              H    H   O  CH.sub.2CHCl.sub.2                                                                           O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 471                                                                              H    H   O  CH.sub.2CCl.sub.3                                                                            O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 472                                                                              H    H   O  CF.sub.2 Cl    O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 473                                                                              H    H   O  CF.sub.2 Br    O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 474                                                                              H    H   S  CHF.sub.2      O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 475                                                                              H    H   S  CF.sub.2CHF.sub.2                                                                            O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 476                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.2                 477                                                                              5-F  H   O  CHF.sub.2      O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 478                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 479                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 480                                                                              5-Cl H   O  CHF.sub.2      O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 481                                                                              H    6-F O  CHF.sub.2      O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 482                                                                              5-OCH.sub.3                                                                        H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 483                                                                              H    3-CH.sub.3                                                                        O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 484                                                                              H    H   O  CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                             O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 485                                                                              H    H   O  CH.sub.2CC(CH.sub.3).sub.2                                                                   O CH OCH.sub.2CF.sub.3                                                                      OCH.sub.2CF.sub.3                 486                                                                              H    H   O  CHF.sub.2      O CH OCHF.sub.2                                                                             OCHF.sub.2    181-182°     487                                                                              H    H   O  CF.sub.3       O CH OCHF.sub. 2                                                                            OCHF.sub.2    193-194°     488                                                                              H    H   O  CF.sub.2CHF.sub.2                                                                            O CH OCHF.sub.2                                                                             OCHF.sub.2    157-158°     489                                                                              H    H   O  CH.sub.2CF.sub.3                                                                             O CH OCHF.sub.2                                                                             OCHF.sub.2                        490                                                                              H    H   O  CClCHCl        O CH OCHF.sub.2                                                                             OCHF.sub.2                        491                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH OCHF.sub.2                                                                             OCHF.sub.2                        492                                                                              H    H   O  CH.sub.2CH.sub.2OCH.sub.3                                                                    O CH OCHF.sub.2                                                                             OCHF.sub.2    137-138°     493                                                                              H    H   O  CF.sub.2CF.sub.3                                                                             O CH OCHF.sub.2                                                                             OCHF.sub.2    197-198°     494                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCHF.sub.2                                                                             OCHF.sub.2                        495                                                                              H    H   O  CH.sub.2 OCH.sub.3                                                                           O CH OCHF.sub.2                                                                             OCHF.sub.2                        496                                                                              H    H   O  CF.sub.2CHClF  O CH OCHF.sub.2                                                                             OCHF.sub.2                        497                                                                              H    H   O  CH.sub.2CHCHCH.sub.3                                                                         O CH OCHF.sub.2                                                                             OCHF.sub.2                        498                                                                              H    H   O  CH.sub.2CHClCH.sub.2 Cl                                                                      O CH OCHF.sub.2                                                                             OCHF.sub.2                        499                                                                              H    H   O  CH(CH.sub.2 Cl).sub.2                                                                        O CH OCHF.sub.2                                                                             OCHF.sub.2                        500                                                                              H    H   O  CH.sub.2CH.sub.2 F                                                                           O CH OCHF.sub.2                                                                             OCHF.sub.2                        501                                                                              H    H   O  CH.sub.2C(CH.sub.3)CH.sub.2                                                                  O CH OCHF.sub.2                                                                             OCHF.sub.2                        502                                                                              H    H   O  CH.sub.2CHCl.sub.2                                                                           O CH OCHF.sub.2                                                                             OCHF.sub.2                        503                                                                              H    H   O  CH.sub.2CCl.sub.3                                                                            O CH OCHF.sub.2                                                                             OCHF.sub.2                        504                                                                              H    H   O  CF.sub.2 Cl    O CH OCHF.sub.2                                                                             OCHF.sub.2                        505                                                                              H    H   O  CF.sub.2 Br    O CH OCHF.sub.2                                                                             OCHF.sub.2                        506                                                                              H    H   S  CHF.sub.2      O CH OCHF.sub.2                                                                             OCHF.sub.2    157-158°     507                                                                              H    H   S  CF.sub.2CHF.sub.2                                                                            O CH OCHF.sub.2                                                                             OCHF.sub.2                        508                                                                              H    H   SO.sub.2                                                                         CHF.sub.2      O CH OCHF.sub.2                                                                             OCHF.sub.2                        509                                                                              5-F  H   O  CHF.sub.2      O CH OCHF.sub.2                                                                             OCHF.sub.2                        510                                                                              5-F  H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCHF.sub.2                                                                             OCHF.sub.2                        511                                                                              H    6-Cl                                                                              O  CHF.sub.2      O CH OCHF.sub.2                                                                             OCHF.sub.2                        512                                                                              5-Cl H   O  CHF.sub.2      O CH OCHF.sub.2                                                                             OCHF.sub.2                        513                                                                              H    6-F O  CHF.sub.2      O CH OCHF.sub.2                                                                             OCHF.sub.2                        514                                                                              5-OCH.sub.3                                                                        H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCHF.sub.2                                                                             OCHF.sub.2                        515                                                                              H    3-CH.sub.3                                                                        O  CH.sub.2CHCH.sub.2                                                                           O CH OCHF.sub.2                                                                             OCHF.sub.2                        516                                                                              H    H   O  CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                             O CH OCHF.sub.2                                                                             OCHF.sub.2                        517                                                                              H    H   O  CH.sub.2CC(CH.sub.3).sub.2                                                                   O CH OCHF.sub.2                                                                             OCHF.sub.2                        518                                                                              H    H   O  CHF.sub.2      O N  CH.sub.3 OCH.sub.2CH.sub.2 Cl                                                                        81°                                                                    (decom-                                                                       position)           519                                                                              H    H   O  CHF.sub.2      O N  CH.sub.3 OCH.sub.2CCl.sub.3                                                                          141-142°     520                                                                              H    H   O  CHF.sub.2      O CH CH.sub.3 OCF.sub.2CHFCl                                                                              167-168°     521                                                                              H    H   O  CHF.sub.2      O CH CH.sub.3 OCF.sub.2CHF.sub.2                                                                          151-152°     522                                                                              H    H   O  CHF.sub.2      O CH CH.sub.3 OCF.sub.2CHFBr                    523                                                                              H    H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                                                                          137-138°                                                               8                   524                                                                              H    H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCF.sub.2 CHFCl                                                                             125-126°                                                               2                   525                                                                              H    H   O  CHF.sub.2      O CH OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              526                                                                              H    H   O  CHF.sub.2      O CH Cl       OCF.sub.2CHF.sub.2                527                                                                              H    H   O  CHF.sub.2      O CH Cl       OCF.sub.2CHFCl                                                                              150-151°     528                                                                              H    H   O  CHF.sub.2      O N  CH.sub.3 OCF.sub.2CHF.sub.2                529                                                                              H    H   O  CHF.sub.2      O N  CH.sub.3 OCF.sub.2CHFCl                    530                                                                              H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                531                                                                              H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCF.sub.2CHFCl                    532                                                                              H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCF.sub.2CHFBr                    533                                                                              H    H   O  CHF.sub.2      O N  OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              534                                                                              H    H   O  CHF.sub.2      O N  C.sub.2 H.sub.5                                                                        OCF.sub.2CHF.sub.2                535                                                                              H    H   O  CF.sub.3       O CH CH.sub.3 OCF.sub.2CHFCl                    536                                                                              H    H   O  CF.sub.3       O CH CH.sub.3 OCF.sub.2CHF.sub.2                537                                                                              H    H   O  CF.sub. 3      O CH CH.sub.3 OCF.sub.2CHFBr                    538                                                                              H    H   O  CF.sub.3       O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                539                                                                              H    H   O  CF.sub.3       O CH OCH.sub.3                                                                              OCF.sub.2CHFCl                    540                                                                              H    H   O  CF.sub.3       O CH OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              541                                                                              H    H   O  CF.sub.3       O CH Cl       OCF.sub.2CHF.sub.2                542                                                                              H    H   O  CF.sub.3       O CH Cl       OCF.sub.2CHFCl                    543                                                                              H    H   O  CF.sub.3       O N  CH.sub.3 OCF.sub.2CHF.sub.2                544                                                                              H    H   O  CF.sub.3       O N  CH.sub.3 OCF.sub.2CHFCl                    545                                                                              H    H   O  CF.sub.3       O N  OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                546                                                                              H    H   O  CF.sub.3       O N  OCH.sub.3                                                                              OCF.sub.2CHFCl                    547                                                                              H    H   O  CF.sub.3       O N  OCH.sub.3                                                                              OCF.sub.2CHFBr                    548                                                                              H    H   O  CF.sub.3       O N  OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              549                                                                              H    H   O  CF.sub.3       O N  C.sub.2 H.sub.5                                                                        OCF.sub.2 CHF.sub.2               550                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCF.sub.2CHFCl                    551                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCF.sub.2CHF.sub.2                552                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH CH.sub.3 OCF.sub.2CHFBr                    553                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                554                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              OCF.sub.2CHFCl                    555                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              556                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH Cl       OCF.sub.2CHF.sub.2                557                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O CH Cl       OCF.sub.2CHFCl                    558                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  CH.sub.3 OCF.sub.2CHF.sub.2                559                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  CH.sub.3 OCF.sub.2CHFCl                    560                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                561                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCF.sub.2CHFCl                    562                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCF.sub.2CHFBr                    563                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              564                                                                              H    H   O  CH.sub.2CHCH.sub.2                                                                           O N  C.sub.2 H.sub.5                                                                        OCF.sub.2CHF.sub.2                565                                                                              H    H   S  CHF.sub.2      O CH CH.sub.3 OCF.sub.2CHFCl                    566                                                                              H    H   S  CHF.sub.2      O CH CH.sub.3 OCF.sub.2CHF.sub.2                567                                                                              H    H   S  CHF.sub.2      O CH CH.sub.3 OCF.sub.2CHFBr                    568                                                                              H    H   S  CHF.sub.2      O CH CH.sub.3 OCF.sub.2CHF.sub.2                569                                                                              H    H   S  CHF.sub.2      O CH OCH.sub.3                                                                              OCF.sub.2CHFCl                    570                                                                              H    H   S  CHF.sub.2      O CH OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              571                                                                              H    H   S  CHF.sub.2      O CH Cl       OCF.sub.2CHF.sub.2                572                                                                              H    H   S  CHF.sub.2      O CH Cl       OCF.sub.2CHFCl                    573                                                                              H    H   S  CHF.sub.2      O N  CH.sub.3 OCF.sub.2CHF.sub.2                574                                                                              H    H   S  CHF.sub.2      O N  CH.sub.3 OCF.sub.2CHFCl                    575                                                                              H    H   S  CHF.sub.2      O N  OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                576                                                                              H    H   S  CHF.sub.2      O N  OCH.sub.3                                                                              OCF.sub.2CHFCl                    577                                                                              H    H   S  CHF.sub.2      O N  OCH.sub.3                                                                              OCF.sub.2CHFBr                    578                                                                              H    H   S  CHF.sub.2      O N  OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              579                                                                              H    H   S  CHF.sub.2      O N  C.sub.2 H.sub.5                                                                        OCF.sub.2CHF.sub.2                580                                                                              H    H   O  CClCHCl        O CH CH.sub.3 OCF.sub.2CHFCl                    581                                                                              H    H   O  CClCHCl        O CH CH.sub.3 OCH.sub.2CHF.sub.2                582                                                                              H    H   O  CClCHCl        O CH CH.sub.3 OCH.sub.2CHFBr                    583                                                                              H    H   O  CClCHCl        O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                584                                                                              H    H   O  CClCHCl        O CH OCH.sub.3                                                                              OCF.sub.2CHFCl                    585                                                                              H    H   O  CClCHCl        O CH OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              586                                                                              H    H   O  CClCHCl        O CH Cl       OCF.sub.2CHF.sub.2                587                                                                              H    H   O  CClCHCl        O CH Cl       OCF.sub.2CHFCl                    588                                                                              H    H   O  CClCHCl        O N  CH.sub.3 OCF.sub.2CHF.sub.2                589                                                                              H    H   O  CClCHCl        O N  CH.sub.3 OCF.sub.2CHFCl                    590                                                                              H    H   O  CClCHCl        O N  OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                591                                                                              H    H   O  CClCHCl        O N  OCH.sub.3                                                                              OCF.sub.2CHFCl                    592                                                                              H    H   O  CClCHCl        O N  OCH.sub.3                                                                              OCF.sub.2CHFBr                    593                                                                              H    H   O  CClCHCl        O N  OCH.sub.3                                                                              OCF.sub.2CHFCF.sub.3              594                                                                              H    H   O  CClCHCl        O N  C.sub.2 H.sub.5                                                                        OCF.sub.2CHF.sub.2                595                                                                              H    H   O  C.sub.2 H.sub.5                                                                              O CH CH.sub.3 OCF.sub.2CHF.sub.2                596                                                                              H    H   O  C.sub.2 H.sub.5                                                                              O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                597                                                                              H    H   O  C.sub.2 H.sub.5                                                                              O CH OCH.sub.3                                                                              OCF.sub.2CHFCl                    598                                                                              H    H   O  C.sub.2 H.sub.5                                                                              O CH CH.sub.3 OCF.sub.2CHFCl                    599                                                                              H    H   O  C.sub.2 H.sub.5                                                                              O N  OCH.sub.3                                                                              OCF.sub.2CHFCl                    600                                                                              H    H   O  C.sub.2 H.sub.5                                                                              O N  OCH.sub.3                                                                              OCF.sub.2CF.sub.2 H               601                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH CH.sub.3 OCF.sub.2CHFCl                    602                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                603                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  CH.sub.3 OCF.sub.2CHF.sub.2                604                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                605                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O N  CH.sub.3 OCF.sub.2CHFCl                    606                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH CH.sub.3  OCF.sub.2CHF.sub.2               607                                                                              H    H   O  CH.sub.2CH.sub.2 Cl                                                                          O CH OCH.sub.3                                                                              OCF.sub.2CHFCl                    608                                                                              H    H   O  O(CH.sub.2).sub.2OCH.sub.3                                                                   O CH CH.sub.3 OCF.sub.2CHFCl                    609                                                                              H    H   O  O(CH.sub.2).sub.3OCH.sub.3                                                                   O CH CH.sub.3 OCF.sub.2CHF.sub.2                610                                                                              H    H   O  O(CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                611                                                                              H    H   O  O(CH.sub.2).sub.2OCH.sub.3                                                                   O CH OCH.sub.3                                                                              OCF.sub.2CHFCl                    612                                                                              H    H   O  O(CH.sub.2).sub.2OCH.sub.3                                                                   O N  CH.sub.3 OCF.sub.2CHFCl                    613                                                                              H    H   O  O(CH.sub.2).sub.2OCH.sub.3                                                                   O N  OCH.sub.3                                                                              OCF.sub.2CHFCl                    614                                                                              H    H   O  (CH.sub.2).sub.2SCH.sub.3                                                                    O CH CH.sub.3 OCHF.sub.2    167-68°      615                                                                              H    H   O  (CH.sub.2).sub.2SCH.sub.3                                                                    O CH OCH.sub.3                                                                              OCHF.sub.2                        616                                                                              H    H   O  (CH.sub.2).sub.2 SCH.sub.3                                                                   O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 617                                                                              H    H   O  (CH.sub.2).sub.2SCH.sub.3                                                                    O CH Cl       OCHF.sub.2                        618                                                                              H    H   O  (CH.sub.2).sub.2SCH.sub.3                                                                    O CH CH.sub.3 OCH.sub.2CF.sub.3                 619                                                                              H    H   O  (CH.sub.2).sub.2SCH.sub.3                                                                    O CH OCHF.sub.2                                                                             OCHF.sub.2                        620                                                                              H    H   O  (CH.sub.2).sub.2SCH.sub.3                                                                    O CH CH.sub.3 OCF.sub.2CHF.sub.2                621                                                                              H    H   O  (CH.sub.2).sub.2SCH.sub.3                                                                    O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                622                                                                              H    H   O  (CH.sub.2).sub.2SCH.sub.3                                                                    O N  OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                623                                                                              H    H   O  (CH.sub.2).sub.2SOCH.sub.3                                                                   O CH CH.sub.3 OCHF.sub.2                        624                                                                              H    H   O  (CH.sub.2).sub.2SOCH.sub.3                                                                   O CH OCH.sub.3                                                                              OCHF.sub.2                        625                                                                              H    H   O  (CH.sub.2).sub.2SOCH.sub.3                                                                   O CH Cl       OCHF.sub.2                        626                                                                              H    H   O  (CH.sub.2).sub.2SOCH.sub. 3                                                                  O CH CH.sub.3 OCH.sub.2CF.sub.3                 627                                                                              H    H   O  (CH.sub.2).sub.2SOCH.sub.3                                                                   O CH OCHF.sub.2                                                                             OCHF.sub.2                        628                                                                              H    H   O  (CH.sub.2).sub.2SOCH.sub.3                                                                   O CH CH.sub.3 OCF.sub.2CHF.sub.2                629                                                                              H    H   O  (CH.sub.2).sub.2SOCH.sub.3                                                                   O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                630                                                                              H    H   O  (CH.sub.2).sub.2SOCH.sub.3                                                                   O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 631                                                                              H    H   O  (CH.sub.2).sub.2SOCH.sub.3                                                                   O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                632                                                                              H    H   O  (CH.sub.2).sub.2SO.sub.2CH.sub.3                                                             O CH CH.sub.3 OCHF.sub.2                        633                                                                              H    H   O  (CH.sub.2).sub.2SO.sub.2CH.sub.3                                                             O CH OCH.sub.3                                                                              OCHF.sub.2                        634                                                                              H    H   O  (CH.sub.2).sub.2SO.sub.2CH.sub.3                                                             O CH Cl       OCHF.sub.2                        635                                                                              H    H   O  (CH.sub.2).sub.2SO.sub.2CH.sub.3                                                             O CH CH.sub.3 OCH.sub.2CF.sub.3                 636                                                                              H    H   O  (CH.sub.2).sub.2SO.sub.2CH.sub.3                                                             O CH OCHF.sub.2                                                                             OCHF.sub.2                        637                                                                              H    H   O  (CH.sub.2).sub.2SO.sub.2CH.sub.3                                                             O CH CH.sub.3 OCF.sub.2CHF.sub.2                638                                                                              H    H   O  (CH.sub.2).sub.2SO.sub.2CH.sub.3                                                             O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                639                                                                              H    H   O  (CH.sub.2).sub.2SO.sub.2CH.sub.3                                                             O N  OCH.sub.3                                                                              OCH.sub.2CF.sub.3                 640                                                                              H    H   O  (CH.sub.2).sub.2SO.sub.2CH.sub.3                                                             O CH OCH.sub.3                                                                              OCF.sub.2CHF.sub.2                __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR13##                                                                                                           Melt-                                                                         ing                                                                           point                                  No. X A           ER.sub.3  R.sub.4    [°C.]                           ______________________________________                                        701 O CHF.sub.2   CH OCH.sub.3                                                                            OCHF.sub.2 148-                                                                          149°                            702 O CHF.sub.2   CH CH.sub.3                                                                             OCHF.sub.2                                        703 O CHF.sub.2   CH Cl     OCHF.sub.2                                        704 O CHF.sub.2   CH CH.sub.3                                                                             OCH.sub.2CF.sub.3                                 705 O CHF.sub.2   NOCH.sub.3                                                                              OCH.sub.2CF.sub.3                                 706 O CF.sub.2CHF.sub.2                                                                         CH OCH.sub.3                                                                            OCHF.sub.2                                        707 O CF.sub.2CHF.sub. 2                                                                        CH CH.sub.3                                                                             OCHF.sub.2                                        708 O CF.sub.2CHF.sub.2                                                                         CH Cl     OCHF.sub.2                                        709 O CF.sub.2CHF.sub.2                                                                         CH CH.sub.3                                                                             OCH.sub.2CF.sub.3                                 710 O CF.sub.2CHF.sub.2                                                                         NOCH.sub.3                                                                              OCH.sub.2CF.sub.3                                 ______________________________________                                    

FORMULATION EXAMPLES EXAMPLE 8 Formulation examples for activesubstances of the formula I (%=percent by weight)

    ______________________________________                                        (a) Wettable powder (a)     (b)     (c)                                       ______________________________________                                        active substance    20%     60%     0.5%                                      Na lignin-sulfonate 5%      5%       5%                                       Na lauryl-sulfate   3%      --      --                                        Na diisobutylnaphthalene-sulfonate                                                                --      6%       6%                                       octylphenol-polyethylene glycol ether                                                             --      2%       2%                                       (7-8 mols of ethylene oxide)                                                  highly disperse silica                                                                            5%      27%     27%                                       kaolin              67%     --      --                                        sodium chloride     --      --      59.5%                                     ______________________________________                                    

The active substance is mixed thoroughly with the adjuvants and themixture is ground well in a suitable mill. Wettable powders are obtainedwhich can be diluted with water to give suspensions of any desiredconcentration.

    ______________________________________                                        (b) Emulsion concentrate                                                                              (a)    (b)                                            ______________________________________                                        active substance        10%    1%                                             octylphenol-polyethylene glycol ether                                                                  3%    3%                                             (4-5 mols of ethylene oxide)                                                  Ca dodecylbenzenesulfonate                                                                             3%    3%                                             castor oil polyglycol ether (36 mols of                                                                4%    4%                                             ethylene oxide)                                                               cyclohexanone           30%    10%                                            xylene mixture          50%    79%                                            ______________________________________                                    

Emulsions of any desired concentration can be prepared from thisconcentrate by dilution with water.

    ______________________________________                                        (c) Dusts         (a)     (b)                                                 ______________________________________                                        active substance   0.1%    1%                                                 talc              99.9%   --                                                  kaolin            --      99%                                                 ______________________________________                                    

Ready-to-use dusts are obtained by mixing the active substance with thecarrier and grinding the mixture on a suitable mill.

    ______________________________________                                        (d) Extruded granules                                                                             (a)    (b)                                                ______________________________________                                        active substance    10%    1%                                                 Na lignin-sulfonate  2%    2%                                                 carboxymethylcellulose                                                                             1%    1%                                                 kaolin              87%    96%                                                ______________________________________                                    

The active substance is mixed with the adjuvants, and the mixture isground and moistened with water. This mixture is extruded and theextruded material is then dried in a stream of air.

    ______________________________________                                        (e) Coated granules                                                           ______________________________________                                        active substance         3%                                                   polyethylene glycol (molecular weight 200)                                                             3%                                                   kaolin                   94%                                                  ______________________________________                                    

The finely ground active substance is uniformly applied to the kaolin,moistened with polyethylene glycol, in a mixer. This gives dust-freecoated granules.

    ______________________________________                                        (f) Suspension concentrate                                                                           (a)      (b)                                           ______________________________________                                        active substance       40%      5%                                            ethylene glycol        10%      10%                                           nonylphenol-polyethylene glycol ether                                                                 6%      1%                                            (15 mols of ethylene oxide)                                                   Na lignin-sulfonate    10%      5%                                            carboxymethylcellulose  1%      1%                                            37% aqueous formaldehyde solution                                                                    0.2%     0.2%                                          silicone oil in the form of a 75% aqueous                                                            0.8%     0.8%                                          emulsion                                                                      water                  32%      77%                                           ______________________________________                                    

The finely ground active substance is intimately mixed with theadjuvants to give a suspension concentrate from which suspensions of anydesired concentration can be prepared by dilution with water.

    ______________________________________                                        (g) Salt solution                                                             ______________________________________                                        active substance       5%                                                     isopropylamine         1%                                                     octylphenol-polyethylene glycol ether                                                                3%                                                     (78 mols of ethylene oxide)                                                   water                  91%                                                    ______________________________________                                    

BIOLOGICAL EXAMPLES EXAMPLE 9 Demonstration of the herbicidal actionbefore emergence of the plants

Plant seeds are sown in flowerpots 12-15 cm in diameter in a greenhouse.Immediately thereafter, the soil surface is treated with an aqueousdispersion or solution of the active substances. Concentrations of 4 kgof active substance per hectare are used. The pots are then kept at atemperature of 22°-25° C. and at 50-70% relative atmospheric humidity inthe greenhouse. The experiment is evaluated after 3 weeks, and theaction on the experimental plants is rated according to the followingscale:

1: Plants have not germinated or have been totally destroyed

2-3: Very powerful action

4-6: Moderate action

7-8: Weak action

9: No action (as untreated control).

    ______________________________________                                        Pre-emergence action                                                          Amount used: 4 kg of active substance/hectare                                 Compound No.                                                                              Avena   Setaria   Sinapis                                                                             Stellaria                                 ______________________________________                                         2          4       3         2     2                                         31          2       1         2     2                                         ______________________________________                                    

EXAMPLE 10 Demonstration of the selectivity in pre-emergence use

In the same experimental design as in Example 9, a larger number ofplant seeds are treated with various amounts of active substance. Theexperiment was evaluated according to the same scale.

    ______________________________________                                        Pre-emergence action:                                                         Action         Compound  Compound  Compound                                   kg of active substance                                                                       No. 1     No. 6     No. 25                                     applied/ha of test plants                                                                    0.06   0.03   0.06 0.03 0.06 0.03                              ______________________________________                                        Wheat          9      9      7    9    9    9                                 Maize          2      6      6    7    9    9                                 Alopecurus myos.                                                                             2      2      4    6    6    6                                 Cyperus escul. 5      6      2    2    4    4                                 Abutilon       3      3      2    3    3    3                                 Chenopodium sp.                                                                              3      3      2    2    3    3                                 Ipomoea        4      8      2    2    8    9                                 Sinapis        2      2      2    2    2    2                                 Galium         4      4      2    2    2    3                                 Viola tricolor 2      2      1    1    2    3                             

EXAMPLE 11 Demonstration of the herbicidal action after emergence of theplants (contact action)

A number of both monocotyledonous and dicotyledonous weeds and cropplants are sprayed, after emergence, in the 4- to 6-leaf stage with anaqueous active substance dispersion in dosages of 4 kg of activesubstance/ha, and are then kept at 24° to 26° C. and at 45-60% relativeatmospheric humidity. The experiment is evaluated 15 days after thetreatment and the plants are rated according to the same scale as in thepre-emergence experiment.

    ______________________________________                                        Post-emergence action                                                         Amount applied: 4 kg of active substance/hectare                              Com-                                                                          pound                       Sol-        Stel-                                                                              Phase-                           No.   Avena   Setaria Lolium                                                                              anum  Sinapis                                                                             laria                                                                              olus                             ______________________________________                                         2    5       2       2     2     2     2    3                                31    2       3       3     2     2     3    3                                ______________________________________                                    

EXAMPLE 12 Demonstration of the selectivity in post-emergence use

In the same experimental design as in Example 11, a larger number ofplants are treated with various amounts of active substance. Theevaluation was carried out according to the scale given in Example 9.

    ______________________________________                                        Post-emergence action                                                         Action           Compound    Compound                                         kg of active substance                                                                         No. 6       No. 25                                           applied/ha of test plants                                                                      0.06   0.03     0.06 0.03                                    ______________________________________                                        Wheat            8      9        9    9                                       Maize            9      9        9    9                                       Dry rice         7      9        9    9                                       Cyperus escul.   3      4        4    4                                       Cotton           9      9        9    9                                       Xanthium sp.     2      2        1    1                                       Chenopodium sp.  3      3        9    9                                       Sinapis          2      3        3    4                                       Galium aparine   1      2        6    7                                       Viola tricolor   3      4        3    4                                       ______________________________________                                    

EXAMPLE 13 Demonstration of the inhibition of sprouting of storedpotatoes

A number of commercially available potatoes of the "Urgenta" varietywithout sprouts are washed and dried. The potatoes are then immersed inactive substance emulsions of various concentrations, in each case forone minute, and are then laid out on filter paper in plastic dishes andkept at temperatures of 14° and 21° C. in the dark at 50% relativeatmospheric humidity. Evaluation was effected 34 days after theapplication. At the same time, the weight loss of the tubers and theweight of sprouts were determined, in comparison with the untreatedcontrol. In this experiment, the compounds according to the inventionshowed complete prevention of sprouting. At the same time, the weightloss of the potatoes was less than 10% of the weight loss of the controlpotatoes.

EXAMPLE 14 Demonstration of the inhibition of growth in tropicalleguminosae cover crops

Test plants of the Psophocarpus palustris and Centrosema pubescensvariety are grown, from cuttings, in plastic dishes containing asoil/peat/sand mixture (1:1:1). After the small plants have taken root,they are repotted in 9 cm pots and watered as required. Furthercultivation of the plants takes place in a greenhouse at a daytimetemperature of 27° C. and a nighttime temperature of 21° C., with a meanperiod of light of 14 hours (6000 lux) and at an atmospheric humidity of70%. The test plants are cut back to a height of about 15 cm and, 7 daysthereafter, are sprayed with a spray liquor of the active substance(calculated as 0.3 or 3 kg of active substance per hectare). 4 weeksafter the application, the growth of the treated plants is compared withthat of control plants which have been pruned but not treated. In thisexperiment, the plants treated with the active substances of the formulaI show a distinct reduction in new additional growth (less than 20% ofthe new additional growth of untreated control plants) without theexperimental plants thereby being damaged.

EXAMPLE 15 Demonstration of pre-emergence selectivity in soybean crops

The experimental plants are sown in sandy/loamy arable soil in plasticcontainers having a capacity of 30 l (60×30×25 cm), and are covered witha layer of soil 1-2 cm deep and watered with water. After one day, theactive substance is applied in the form of an aqueous spray liquor in anamount corresponding to 500 l/ha and in concentrations corresponding to60 g/ha and 30 g/ha. The containers are then kept in a greenhouse attemperatures of 20°-25° C. and are watered as required. After 33 days,the experiment is evaluated and the plants are rated according to thesame scale as in Example 9.

    ______________________________________                                        Pre-emergence action in soybean crops                                         Active substance No. 31                                                                      Amount applied                                                 Experimental plants                                                                            0.06 kg/ha                                                                              0.03 kg/ha                                         ______________________________________                                        Soybean          7         8                                                  Amaranthus ret.  2         3                                                  Ipomoea p.       3         4                                                  Portulaca o.     1         2                                                  Brachiaria pl.   3         4                                                  Xanthium can.    3         3                                                  ______________________________________                                    

EXAMPLE 16 Growth regulation of soybeans

Soybeans of the "Hark" variety are sown in a soil/peat/sand mixture inthe ratio 6:3:1 in plastic containers and are placed in a climaticallycontrolled chamber. As a result of optimum selection of the temperature,illumination, addition of fertiliser and watering, the plants havedeveloped as far as the 5-6 trifoliate-leaf stage after about 5 weeks.At this point in time, the plants are sprayed with the aqueous liquor ofan active substance of the formula I until thoroughly wet. Theconcentration is up to 100 g of active substance/ha. The evaluation iseffected about 5 weeks after application of the active substance. Theactive substances of the formula I according to the invention cause anoticeable increase in the number and weight of silicles on the mainstem in comparison with the untreated control plants.

    ______________________________________                                        Growth-regulating action in soybean crops                                     Active substance No. 31                                                                          Number of silicles                                                                         Weight of silicles                            Amount Height of plants                                                                          on the main stem                                                                           on the main stem                              applied                                                                              in % relative                                                                             in % relative                                                                              in % relative                                 g/ha   to the control                                                                            to the control                                                                             to the control                                ______________________________________                                         3     100         130          124                                           10     99          115          106                                           30     99          110          100                                           100    89          115          112                                           ______________________________________                                    

What is claimed is:
 1. A compound of the formula: ##STR14## wherein Z isO or S;X is O, S, SO or SO₂ ; A is (i) halogenated alkyl or halogenatedalkenyl of up to 6 carbon atoms or (ii) alkyl or alkenyl of up to 6carbon atoms substituted with an unhalogenated or halogenated alkoxy,alkylthio, alkylsulfinyl or alkylsulfonyl group of up to 4 carbon atoms;R₁ is hydrogen, halo, alkyl of up to 5 carbon atoms, or R₅ --Y-- inwhich Y is O, S, SO or SO₂ ; and R₅ is an alkyl, alkenyl or alkynylgroup of up to 5 carbon atoms; R₂ is hydrogen, halo, alkyl of up to 5carbon atoms, haloalkyl of up to 5 carbon atoms, R₅ --Y-- in which Y andR₅ are as defined above, nitro, R₆ OCO-- or R₇ R₈ NCO--, in which R₆ isan alkyl, alkenyl, or alkynyl group of up to 5 carbon atoms; and each ofR₇ and R₈ are hydrogen or an alkyl, alkenyl or alkynyl group of up to 5carbon atoms; R₃ is hydrogen, halo, alkyl of up to 4 carbon atoms,alkoxy of up to 4 carbon atoms, alkylthio of up to 4 carbon atoms,haloalkyl of up to 4 carbon atoms, haloalkoxy of up to 4 carbon atoms,or alkoxyalkyl of up to 4 carbon atoms; and R₄ is halogenated alkoxy orhalogenated alkylthio of up to 4 carbon atoms.
 2. A compound accordingto claim 1 whereinZ is O; X is O; one of R₁ and R₂ is hydrogen and theother of R₁ and R₂ is hydrogen, chloro or fluoro; R₃ is methyl, ethyl,methoxy, chloro, trifluormethyl, halomethoxy or haloethoxy; and R₄ ishalomethoxy or haloethoxy.
 3. A compound according to claim 2 wherein Ais halogenated methyl or halogenated ethyl.
 4. A compound according toclaim 3 wherein R₄ is difluoromethoxy or 2,2,2-trifluoroethoxy. 5.N-(2-Difluoromethoxyphenyl-sulfonyl)-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]-ureaaccording to claim
 1. 6. A herbicidal and growth-regulating compositionwhich comprises an effective amount of at least one compound accordingto claim 1, together with a suitable carrier therefor.
 7. A method ofcontrolling undesired plant growth, which method comprises applyingthereto or to the locus thereof a herbicidally effective amount of acompound according to claim
 1. 8. A method of regulating plant growth inorder to achieve greater yields, which method comprises applying theretoor the locus thereof an effective amount of a compound according toclaim
 1. 9.N-[2-(2-Chloroethoxy)-phenyl-sulfonyl]-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]-ureaaccording to claim
 1. 10. A compound according to claim 4 wherein A isdifluoromethyl or 2-chloroethyl.
 11. A compound according to claim 10,in which R₄ is the 2,2,2-trifluoroethoxy radical.
 12. A compoundaccording to claim 10, in which R₄ is the difluoromethoxy radical.
 13. Acompound of the formula: ##STR15## wherein Z is O or S;A is alkenyl ofup to 6 carbon atoms; R₁ is hydrogen, halo, alkyl of up to 5 carbonatoms, or R₅ --Y-- in which Y is O, S, SO or SO₂ ; and R₅ is an alkyl,alkenyl or alkynyl group of up to 5 carbon atoms; R₂ is hydrogen, halo,alkyl of up to 5 carbon atoms, haloalkyl of up to 5 carbon atoms, R₅--Y-- in which Y and R₅ are as defined above, nitro, R₆ OCO-- or R₇ R₈NCO--, in which R₆ is an alkyl, alkenyl, or alkynyl group of up to 5carbon atoms; and each of R₇ and R₈ are hydrogen or an alkyl, alkenyl oralkynyl group of up to 5 carbon atoms; R₃ is hydrogen, halo, alkyl of upto 4 carbon atoms, alkoxy of up to 4 carbon atoms, alkylthio of up to 4carbon atoms, haloalkyl of up to 4 carbon atoms, haloalkoxy of up to 4carbon atoms or alkoxyalkyl of up to 4 carbon atoms; and R₄ ishalogenated alkoxy or halogenated alkylthio or up to 4 carbon atoms. 14.A compound according to claim 13 whereinZ is O; one of R₁ and R₂ ishydrogen and the other of R₁ and R₂ is hydrogen, chloro or fluoro; R₃ ismethyl, ethyl, methoxy, chloro, trifluoromethyl, halomethoxy orhaloethoxy; and R₄ is halomethoxy or haloethoxy.
 15. A compoundaccording to claim 14 wherein R₄ is difluoromethoxy or2,2,2-trifluoroethoxy.
 16. A herbicidal and growth-regulatingcomposition which comprises an effective amount of at least one compoundaccording to claim 13, together with a suitable carrier therefor.
 17. Amethod of controlling undesired plant growth which comprises applying tothe plant or to the locus of its growth a herbicidally effective amountof a compound according to claim
 13. 18. A method regulating plantgrowth in order to achieve greater yields, which method comprisesapplying to the plant or the locus of its growth an effective amount ofa compound according to claim 13.